Device for removing refractory organic pollutants in water

Abstract

The utility model relates to a device for removing refractory organic pollutants in water, which comprises a sewage inlet pipe, a medicament A adding system, a medicament B adding system, a micro-nano bubble generator and a reaction tower, the reaction tower is sequentially provided with a sewage distribution pipe, a micro-nano bubble release pipe, an electrode plate, a three-phase separator, a membrane component and a water outlet pipe from bottom to top, the sewage distribution pipe, the medicament A adding system and the medicament B adding system are respectively connected with the sewage inlet pipe, the micro-nano bubble release pipe is connected with the micro-nano bubble generator, and the water outlet pipe is connected with the membrane component. By designing the novel device for removing the refractory organic pollutants in the water, better equipment and method can be obtained aiming at the defects of the existing problem of treating the refractory organic pollutants in the water. The refractory organic pollutants or new pollutants in the wastewater are mineralized into carbon dioxide and water or biochemically-degradable small molecular organic matters under the action of the oxyradicals.

Description

TECHNICAL FIELD

[0001] The utility model relates to a kind of pollution removal devices, in particular to a kind of device for removing water in difficult degradable organic pollutants. BACKGROUND

[0002] In recent years, with the acceleration of industrialization and changes in lifestyle, the number of difficult degradable organic pollutants and new pollutants in water bodies is increasing, posing a serious threat to the ecological environment and human health. Traditional water treatment technologies, such as coagulation, sedimentation, and biological treatment, often fail to effectively remove these pollutants, especially new pollutants such as endocrine disruptors, microplastics, and pharmaceutical residues, which are complex, hidden, and persistent, posing long-term potential risks to the environment and human health. Therefore, there is an urgent need to develop an efficient, economical, and environmentally friendly water treatment technology to address the current water pollution treatment dilemma.

[0003] To date, there are several methods for treating difficult degradable organic pollutants / new pollutants, such as Fenton method, Fenton-like method, internal electrolysis method, activated persulfate method, incineration method, multi-effect evaporation method, and sodium bismuthate oxidation method. These methods are not very good in terms of cost, safety, or efficiency. Therefore, new and effective methods and devices are needed for pollution reduction. SUMMARY

[0004] The technical problem to be solved by the utility model is to provide a device for removing water in difficult degradable organic pollutants.

[0005] The technical solution to solve the above technical problems is a device for removing water in difficult degradable organic pollutants, comprising a sewage inlet pipe, a medicament A dosing system, a medicament B dosing system, a micro-nano bubble generator, and a reaction tower. The reaction tower is sequentially provided with a sewage distribution pipe, a micro-nano bubble release pipe, an electrode plate, a three-phase separator, a membrane module, and a water outlet pipe from bottom to top. The sewage distribution pipe, medicament A dosing system, and medicament B dosing system are connected to the sewage inlet pipe. The micro-nano bubble release pipe is connected to the micro-nano bubble generator. The water outlet pipe is connected to the membrane module.

[0006] The further technical solution of the utility model is that the electrode plates are arranged in an alternating positive and negative electrode manner, with the positive electrode being a graphite electrode and the negative electrode being a titanium plate electrode. The spacing between the electrode plates is 5-15 cm. The positive electrode is connected to the positive electrode of a low-voltage direct current charger, and the negative electrode is connected to the negative electrode of the low-voltage direct current charger. The output voltage of the low-voltage direct current charger is set to 5-25 V.

[0007] The three-phase separator is composed of a plurality of triangular groove plates, the top angle of the triangular groove plate is 60-80°, the vertical height of the triangular groove plate is 20-30 cm, and the gas collection area at the top angle of the triangular groove plate is provided with an exhaust hole. The three-phase separator is composed of triangular groove plates arranged to form a layer of triangular groove plates, and the three-phase separator is provided with a plurality of layers of triangular groove plates from bottom to top, and the upper and lower layers of triangular groove plates are arranged and installed in a staggered peak manner, and the horizontal projection distance of the gap between the upper and lower layers of triangular groove plates is 5-15 cm.

[0008] The membrane module is composed of a filamentous hollow fiber membrane, the membrane module is immersed below the liquid surface of the reaction tower by at least 30 cm, the pore size of the filamentous hollow fiber membrane is less than 0.1 μm, a water production pressure gauge and a water production pump are respectively arranged on the water outlet pipe connected with the membrane module, the membrane module forms negative pressure under the action of the water production pump, and the treated wastewater is discharged after being filtered by the membrane module under negative pressure.

[0009] The micro-nano bubble release pipe is provided with a spiral release device, and each spiral release device serves an area of 0.1-0.2 m 2 . With each spiral release device as the center, the area served around is 0.1-0.2 m 2 , and accordingly the number of release devices required for a plane can be estimated (plane area ÷ (0.1-0.2 m 2 ) = number of release devices.

[0010] The medicament A adding system and the medicament B adding system are respectively connected with the sewage inlet pipe through a pipeline mixer, the sewage inlet pipe is provided with a sewage lifting pump and a water inlet flowmeter, and the water inlet flowmeter is a metering pump. The sewage transmission can be quantitatively performed through the water inlet flowmeter. The upper end of the reaction tower is provided with a liquid level controller, the liquid level controller is located above the three-phase separator, the sewage lifting pump is interlocked with the liquid level controller, the liquid level controller can be used to control the height of the liquid in the reaction tower, the sewage lifting pump is started when the liquid level controller is at a low liquid level, and the sewage lifting pump is stopped when the liquid level controller is at a high liquid level.

[0011] The medicament A adding system comprises a medicament dissolving tank A, a metering pump A and an ORP meter, the ORP meter is arranged on the reaction tower, the sensing end of the ORP meter is located above the electrode plate in the reaction tower, the metering pump A is arranged on the medicament dissolving tank A and connected with the sewage inlet pipe, the metering pump A is interlocked with the ORP meter on the upper part of the electrode plate in the reaction tower, the metering pump A is started when the ORP is less than 500 mV, and the metering pump A is stopped when the ORP is greater than 800 mV. The medicament B adding system comprises a medicament dissolving tank B, a metering pump B and a time relay, the metering pump B is arranged on the medicament dissolving tank B and connected with the sewage inlet pipe, and the metering pump is interlocked with the time relay to realize automatic starting and stopping. The electrode plate is arranged at a position 10-20 cm directly above the micro-nano bubble release pipe, the electrode plate is connected with a low-voltage direct-current charging machine, the three-phase separator is arranged at a position 30-50 cm directly above the electrode plate, and the membrane module is arranged at a position 30-50 cm directly above the three-phase separator.

[0012] Due to the adoption of the technical scheme, the device for removing the refractory organic pollutants in water has the following beneficial effects:

[0013] 1. The device for removing the refractory organic pollutants in water is designed, and the device can solve the problems of the existing device for removing the refractory organic pollutants in water, and a better device and method are obtained. The medicament adding device adds medicaments in the reaction tower for sewage treatment, and the medicaments A and B and the continuous flow membrane chemical reactor generate oxidation free radicals. The refractory organic pollutants or new pollutants in the wastewater are mineralized into carbon dioxide and water or small-molecule organic matters which can be biodegraded under the action of the oxidation free radicals.

[0014] 2. The reaction tower of the device is provided with a three-phase separator and a filamentous hollow fiber membrane, and the residual coagulation and precipitation are carried out, so that the pollution yield is reduced and the land is saved. The three-phase separator is introduced into the reaction tower, the filtration pressure of the filamentous hollow fiber membrane is reduced, and the regeneration cycle and service life of the filamentous hollow fiber membrane are prolonged.

[0015] In the following, the technical features of the device for removing the refractory organic pollutants in water will be further described in combination with the drawings and specific embodiments. DRAWINGS

[0016] Figure 1 : a structure diagram of the device for removing the refractory organic pollutants in water.

[0017] Figure 2 : a layout diagram of the sewage distribution pipe.

[0018] Figure 3 : a layout diagram of the micro-nano bubble releasing pipe.

[0019] Figure 4 : a layout diagram of the electrode plate in a top view state.

[0020] Figure 5 : a structure diagram of the electrode plate support.

[0021] Figure 6 : a structure diagram of the three-phase separator.

[0022] Figure 7 : a top view state diagram of the three-phase separator.

[0023] Figure 8 : a top view diagram of the three-phase separator support.

[0024] Figure 9 : a structure diagram of the electrode plate support.

[0025] Figure 10Structure diagram of the medicament A dosing system.

[0026] Figure 11 Structure diagram of the medicament B dosing system.

[0027] Figure 12 Structure diagram of the triangular groove plate of the three-phase separator.

[0028] In the above figures, the following numbers are explained as follows:

[0029] 1 - sewage inlet, 2 - sewage lifting pump, 3 - water inlet flow meter, 4 - pipeline mixer A, 5 - medicament A dosing system, 6 - pipeline mixer B, 7 - medicament B dosing system, 8 - micro-nano bubble generator, 9 - sewage distribution pipe, 10 - micro-nano bubble release pipe, 11 - electrode plate support bracket, 12 - cathode, 13 - anode, 14 - ORP meter, 15 - three-phase separator support bracket, 16 - three-phase separator, 17 - three-phase separator exhaust vertical pipe, 18 - liquid level controller, 19 - membrane module, 20 - pressure gauge, 21 - water production pump, 22 - water production flow meter, 23 - low-voltage DC charger, 24 - slag discharge port, 25 - triangular groove plate of the three-phase separator, 26 - exhaust pipe, 27 - continuous flow membrane chemical reactor (CF-MCR), 28 - spiral release device, 29 - electrode plate clamping groove, 30 - medicament tank A, 31 - metering pump A, 32 - medicament tank B, 33 - metering pump B, A - top angle of the triangular groove plate. DETAILED DESCRIPTION

[0030] The device for removing refractory organic pollutants in water comprises a sewage inlet pipe, a medicament A dosing system, a medicament B dosing system, a micro-nano bubble generator and a reaction tower, the reaction tower is sequentially provided with a sewage distribution pipe, a micro-nano bubble release pipe, an electrode plate, a three-phase separator, a membrane module and a water outlet pipe from bottom to top, the sewage distribution pipe, the medicament A dosing system and the medicament B dosing system are connected with the sewage inlet pipe, the micro-nano bubble release pipe is connected with the micro-nano bubble generator, and the water outlet pipe is connected with the membrane module.

[0031] The medicament A dosing system and the medicament B dosing system are respectively connected with the sewage inlet pipe through pipeline mixers, the sewage inlet pipe is provided with a sewage lifting pump and a water inlet flow meter, the water inlet flow meter is a metering pump, the sewage lifting pump is connected with a sewage source through a sewage inlet of the sewage lifting pump, sewage is transported into the reaction tower through the sewage lifting pump, sewage transmission can be quantitatively carried out through the water inlet flow meter, the pipeline mixers include a first pipeline mixer and a second pipeline mixer, the two pipeline mixers are respectively arranged on the sewage inlet pipe and connected with corresponding medicament tanks.

[0032] The micro-nano bubble release pipe is provided with a spiral release device, the service area of each spiral release device is 0.1-0.2m 2. With each spiral releaser as the center, the service area is 0.1-0.2m 2 , so the number of releasers needed for a plane can be estimated (plane area ÷ (0.1-0.2m 2 ) ) = number of releasers. The wastewater is transported by the sewage lifting pump to the reaction tower, and reagent A and reagent B are added during the transportation, and then the reaction and decomposition are carried out in the reaction tower, and then electrolysis and filtration are carried out, and finally the treated wastewater is discharged from the drain pipe by the water production pump.

[0033] The bottom of the reaction tower is provided with a slag discharge port, the lower end of the reaction tower 27 is distributed with a sewage distribution pipe 9, and a micro-nano bubble release pipe 10 is located above the sewage distribution pipe 9. The electrode plate is arranged 10-20 cm above the micro-nano bubble release pipe 10, and the electrode plate is connected with the low-voltage direct-current charger. The three-phase separator is arranged 30-50 cm above the electrode plate. The membrane assembly is arranged 30-50 cm above the three-phase separator. The upper end of the reaction tower is provided with a liquid level controller, the liquid level controller is located above the three-phase separator, the sewage lifting pump is interlocked with the liquid level controller, and the liquid level controller can be used to control the height of the liquid in the reaction tower. When the liquid level controller is at a low liquid level, the sewage lifting pump starts, and when the liquid level controller is at a high liquid level, the sewage lifting pump stops.

[0034] The reagent A dosing system comprises a reagent dissolving tank A, a metering pump A and an ORP meter, the ORP meter is arranged on the reaction tower, the sensing end of the ORP meter is located above the electrode plate in the reaction tower, the metering pump A is arranged on the reagent dissolving tank A and connected with the sewage inlet pipe, and the metering pump A is interlocked with the ORP meter on the upper part of the electrode plate in the reaction tower, and the metering pump A starts when the ORP is less than 500 mV; the metering pump A stops when the ORP is greater than 800 mV. The reagent B dosing system comprises a reagent dissolving tank B, a metering pump B and a time relay, the metering pump B is arranged on the reagent dissolving tank B and connected with the sewage inlet pipe, and the metering pump is interlocked with the time relay to realize automatic starting and stopping. The time relay is installed in the electric control cabinet, and when the set time is reached, the metering stops or starts. The difference between the A dosing system and the B dosing system is that the starting and stopping modes are different.

[0035] The electrode plate is arranged in the reaction tower 27 through the electrode plate support bracket, the electrode plates are arranged in an alternating manner of positive electrode and negative electrode, the positive electrode is a graphite electrode, and the negative electrode is a titanium plate electrode. The spacing between the electrode plates is 5-15 cm, the positive electrode is connected with the positive electrode of the low-voltage direct-current charger, the negative electrode is connected with the negative electrode of the low-voltage direct-current charger, and the output voltage of the low-voltage direct-current charger is set to 5-25 V.

[0036] The three-phase separator 16 is arranged in the reaction tower 27 through the three-phase separator support bracket 15, and is composed of a plurality of triangular groove plates. The triangular groove plate is a triangular structure formed by connecting two plates. The top angle A of the triangular groove plate is 60-80°. The vertical height of the triangular groove plate is 20-30 cm. The gas collection area of the top angle of the triangular groove plate is provided with an exhaust hole. An exhaust pipe is arranged at the exhaust hole. The three-phase separator is arranged by triangular groove plates. The triangular groove plates are arranged and placed to form a layer of triangular groove plates. The three-phase separator 16 is provided with a plurality of layers of triangular groove plates from bottom to top. The upper and lower layers of triangular groove plates are arranged and installed in a staggered peak manner. The horizontal projection distance of the gap between the upper and lower layers of triangular groove plates is 5-15 cm. Each layer of triangular groove plates is directly connected through a connecting rod. The exhaust pipes at the top angles of the triangular groove plates of each layer are connected in series and discharged through the exhaust vertical pipe 17. In the embodiment, the three-phase separator is composed of two layers of triangular groove plates. The two layers of triangular groove plates are installed in a staggered peak manner. The horizontal projection distance of the gap between the upper and lower layers of triangular groove plates is 5-15 cm.

[0037] The working principle of the three-phase separator 16 is as follows: The wastewater decomposed in the reaction tower 27, the carbon dioxide, the sewage, the particle medicament B attached with gas and the gas released by the micro-nano bubble generator enter the three-phase separator 16. The gas enters the gas collection area of the top angle of the triangular groove plate 25. The particle medicament B attached with gas is separated from the gas in the process of collision with the three-phase separator 16 and mutual collision. After the separation, the gas enters the gas collection area of the top angle of the triangular groove plate 25. The particle medicament B is settled back to the electrode plate negative pole 12 and the positive pole 13 reaction area. The exhaust holes of the gas collection areas of the top angles of the triangular groove plates 25 are connected in series and discharge the gas through the exhaust vertical pipe 17 arranged on the three-phase separator.

[0038] The membrane assembly is composed of filamentous hollow fiber membranes. The membrane assembly is immersed below the liquid surface of the reaction tower by at least 30 cm. The pore size of the filamentous hollow fiber membranes is less than 0.1 μm. The water production pressure gauge and the water production pump are respectively arranged on the water outlet pipe connected with the membrane assembly. The membrane assembly forms negative pressure under the action of the water production pump. The treated wastewater is discharged after being filtered by the membrane assembly under negative pressure.

[0039] The membrane assembly, the pipeline mixer and the spiral release device can be the existing devices.

[0040] The medicament A is monopersulfate. The medicament A is one or both of monopersulfate potassium and monopersulfate sodium. The medicament B comprises the following components in a mass fraction ratio: 1 part of nano bismuth sodium, 1.5-2 parts of anhydrous ethanol, 1 part of hydroxylated multi-walled carbon nanotubes, 1-2 parts of 65%-80% hydrochloric acid solution, 1 part of 10%-30% sodium acetate solution, 1 part of polyphenylacetylene, and 1.5-2.5 parts of tetrahydrofuran according to a mass ratio.

[0041] The preparation method of the medicament B is as follows: under normal temperature and pressure:

[0042] Step A. Mix nano-sodium bismuthate with anhydrous ethanol at a mass ratio of 1:1.5-2 and ultrasonically dissolve for 5-10 min to obtain a nano-sodium bismuthate dispersion;

[0043] Step B. Mix hydroxylated multi-walled carbon nanotubes with a 65%-80% hydrochloric acid solution at a mass ratio of 1:1-2 and ultrasonically dissolve for 30-60 min, then obtain acidified hydroxylated multi-walled carbon nanotubes by suction filtration, deionized water washing and drying;

[0044] Step C. Mix the acidified hydroxylated multi-walled carbon nanotubes obtained in Step B with the nano-sodium bismuthate dispersion obtained in Step A at a mass ratio of 1:1-1.2 and ultrasonically dissolve for 60-120 min, then obtain sodium bismuthate-hydroxylated multi-walled carbon nanotubes by suction filtration, washing with deionized water and ethylene glycol two or more times, and drying;

[0045] Step D. Mix the sodium bismuthate-hydroxylated multi-walled carbon nanotubes obtained in Step C with a 10%-30% mass fraction sodium acetate solution in deionized water at a mass ratio of 1:1-1.5 and ultrasonically disperse for 30-60 min to obtain sodium acetate-sodium bismuthate-hydroxylated multi-walled carbon nanotubes;

[0046] Step E. Mix polyphenylenevinylene with tetrahydrofuran at a mass ratio of 1:1.5-2.5 and ultrasonically disperse for 60-120 min to obtain a solution of polyphenylenevinylene-tetrahydrofuran;

[0047] Step F. Mix the solution of polyphenylenevinylene-tetrahydrofuran obtained in Step E with the sodium acetate-sodium bismuthate-hydroxylated multi-walled carbon nanotubes in Step D at a mass ratio of 1.1-1.2:1 and ultrasonically disperse for 30-60 min, then inject the obtained solution into a spray dryer, dry at a temperature of 120-200℃, and spray at a pressure of 30-40 MPa to obtain sodium bismuthate-hydroxylated multi-walled carbon nanotube particulate material, i.e., medicament B.

[0048] The suction filtration, washing and drying in the preparation process are all conventional operations.

Claims

1. An apparatus for removing recalcitrant organic pollutants from water, characterized by: The sewage inlet pipe, the medicament A adding system, the medicament B adding system, the micro-nano bubble generator and the reaction tower are included.

2. The device for removing recalcitrant organic pollutants from water according to claim 1, characterized in that: The electrode plates are arranged in an alternating positive and negative electrode mode, the positive electrode is a graphite electrode, the negative electrode is a titanium plate electrode, the spacing between the electrode plates is 5-15 cm, the positive electrode is connected with the positive electrode of the low-voltage direct current charger, the negative electrode is connected with the negative electrode of the low-voltage direct current charger, and the output voltage of the low-voltage direct current charger is set to 5-25 V.

3. The device for removing recalcitrant organic pollutants from water according to claim 1, wherein: The three-phase separator is composed of a plurality of triangular groove plates, the top angle of the triangular groove plate is 60-80°, the vertical height of the triangular groove plate is 20-30 cm, and the gas collection area of the top angle of the triangular groove plate is provided with an exhaust hole.

4. The device for removing recalcitrant organic pollutants from water according to claim 3, characterized in that: The three-phase separator is composed of triangular groove plates arranged to form a layer of triangular groove plates, and the three-phase separator is provided with a plurality of layers of triangular groove plates from bottom to top, and the upper and lower layers of triangular groove plates are arranged and installed in a staggered peak manner, and the horizontal projection distance of the gap between the upper and lower layers of triangular groove plates is 5-15 cm.

5. The device for removing recalcitrant organic pollutants from water according to claim 1, wherein: The membrane assembly is composed of filamentous hollow fiber membranes, the membrane assembly is immersed at least 30 cm below the liquid level of the reaction tower, the pore size of the filamentous hollow fiber membranes is less than 0.1 μm, and a water production pressure gauge and a water production pump are respectively arranged on the water outlet pipe connected with the membrane assembly.

6. The device for removing recalcitrant organic pollutants from water according to claim 1, wherein: The medicament A adding system and the medicament B adding system are respectively connected with the sewage inlet pipe through a pipeline mixer, and a sewage lifting pump and a water inlet flowmeter are arranged on the sewage inlet pipe.

7. The device for removing recalcitrant organic pollutants from water according to claim 6, characterized in that: The medicament A adding system includes a medicament tank A, a metering pump A and an ORP meter, the ORP meter is arranged on the reaction tower, the sensing end of the ORP meter is located above the electrode plate in the reaction tower, the metering pump A is interlocked with the ORP meter on the upper part of the electrode plate in the reaction tower, and the metering pump A is started when the ORP is less than 500 mV; and the metering pump A is stopped when the ORP is greater than 800 mV.

8. The device for removing recalcitrant organic pollutants from water according to claim 6, wherein: The medicament B adding system includes a medicament tank B, a metering pump B and a time relay, the metering pump is interlocked with the time relay to realize automatic starting and stopping.

9. The device for removing recalcitrant organic pollutants from water according to claim 1, wherein: The electrode plate is arranged 10-20 cm above the micro-nano bubble release pipe, and the electrode plate is connected with the low-voltage direct current charger; the three-phase separator is arranged 30-50 cm above the electrode plate; and the membrane assembly is arranged 30-50 cm above the three-phase separator.

10. The device for removing recalcitrant organic pollutants from water according to claim 1, wherein: A liquid level controller is arranged at the upper end of the reaction tower, and the liquid level controller is located above the three-phase separator.

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