CN110589939A - Three-dimensional funnel type electric Fenton device and degradation-resistant organic wastewater treatment method - Google Patents
Three-dimensional funnel type electric Fenton device and degradation-resistant organic wastewater treatment method Download PDFInfo
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- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/467—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction
- C02F1/4672—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction by electrooxydation
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Abstract
A three-dimensional funnel type electric Fenton device and a method for treating refractory organic wastewater. The funnel type carrier is used as a main place for degrading pollutants by three-dimensional electric Fenton while bearing the catalytic particle electrodes, the integrity, continuity and stability advantages of the whole system are exerted, and the funnel type carrier has high-efficiency degradation capability on organic pollutants which are difficult to degrade.
Description
Technical Field
The invention belongs to the field of treatment of refractory organic wastewater, and particularly relates to a three-dimensional funnel type electric Fenton device and a refractory organic wastewater treatment method.
Background
The traditional Fenton method is an advanced oxidation treatment technology, divalent iron ions react with hydrogen peroxide to generate a substance with strong oxidizing property, namely hydroxyl free radicals, the oxidizing property of the substance is only second to the strongest oxidizing fluorine in the nature, the substance has no biotoxicity, the treatment of refractory organic pollutants is highly effective, the cost is low, a device is simple and easy to operate, and the substance is a hot topic in the field of sewage and wastewater treatment at present, but the traditional Fenton reaction mainly has the following three problems: firstly, the reaction efficiency is low under neutral or alkaline conditions, so that a good treatment effect can be obtained only by controlling the reaction pH to be about 3, but a long-time acidic environment can cause a certain degree of corrosion to reaction equipment, and the reaction device needs to be inspected irregularly; secondly, excessive ferric hydroxide precipitates (iron mud) generated in the reaction process and after the reaction easily cause water inlet blockage, and simultaneously prevent Fenton reagents from contacting with each other to influence the reaction, and the iron mud needs to be further effectively treated; thirdly, the relative adding amount of ferrous ions and hydrogen peroxide is not easy to control, hydroxyl free radicals generated by reaction can be consumed if the iron ions are added too much, and the hydrogen peroxide can be wasted if the iron ions are added too little, so that the operation cost of an enterprise is increased, and the generation amount of the hydroxyl free radicals can hardly reach the expected effect.
The three-dimensional electric Fenton method is used for connecting current to the cathode and the anode, so that catalytic particle electrodes filled between the cathode and the anode plates are polarized into particle electrodes with cathode and anode properties, hydrogen peroxide is generated at the cathode through aeration, and meanwhile, the cyclic regeneration of iron catalytic active species from trivalent reduction to divalent reduction is realized; in the anode area, the iron oxide on the catalytic particle electrode participates in the decomposition of the hydrogen peroxide in the role of a catalyst, and compared with the traditional Fenton reaction, the three-dimensional electric Fenton method has the following advantages: the reactant is automatically generated by the system without additional adding; the reactor has high space utilization rate, high current efficiency and high pollutant removal efficiency, and the (electrochemical) reaction extends from the surface of the two-dimensional electrode to the three-dimensional space of the reactor; the reaction process is insensitive to pH change, the high-efficiency pH range can be widened to 3-7, and iron precipitation is not easy to generate to cause pipe orifice blockage; the reaction process is continuous and is suitable for water plants, factories and the like which require continuous operation.
In order to improve the problems of unsatisfactory mixing effect, easy short flow in the operation process and the like of the three-dimensional electro-Fenton method, CN204848373U provides a novel three-dimensional electro-Fenton water treatment device, wherein a cylindrical anode plate is arranged in a reactor, so that the polar plates are repeatedly washed by gas and carriers, the scaling phenomenon of the polar plates is effectively avoided in the use process, and the continuous and effective operation of the device is ensured; CN202576054U has then set up the reactor of toper end to set up the lye tank and handle pungent gas, but above setting has a lot of deficiencies, goes into to be difficult to control electrode polar plate interval, has the difficulty to operating parameter's adjustment when aiming at different kinds of pollutant or pollution concentration, and the mode of flow is difficult to control in this kind of setting simultaneously in the device, can cause the inhomogeneous scheduling problem of water quality treatment, is difficult to realize the abundant mass transfer of gas and water, and the operating efficiency is low.
Disclosure of Invention
The invention provides a high-efficiency three-dimensional electric Fenton reaction device, and mainly aims to strengthen the effective current among particle electrodes in three-dimensional electric Fenton, and ensure that the particle electrodes are in a suspension flowing state through aeration in a funnel type particle carrier, so that the catalytic particle electrodes are in full contact with pollutants to exert the efficiency of the three-dimensional electrodes.
Specific implementation methods are provided for the overall thought.
The three-dimensional funnel type electric Fenton reaction device comprises a cylindrical electrolytic reactor 1, an electrode plate clamp 2, an anode plate 3, a cathode plate 4, a metal working clamp 5, a cylindrical scale 6, a polar plate slide rail 7, a funnel type particle carrier 8, an aeration stone 9, an aerator 10, an air inlet 11, a micro water delivery pump 12, a spiral water distributor 13, a drainage weir 14 and a water outlet 15, wherein the top of the cylindrical electrolytic reactor 1 is open; the funnel type particle carrier 8 is arranged at the middle upper part of the cylindrical electrolytic reactor, the polar plate slide rail 7 is arranged at the top of the funnel type particle carrier, the lower part of the electrode clamping plate 2 is embedded into the polar plate slide rail 7, the polar plate slide rail is an I-shaped slide rail, a power line is connected into the polar plate through the metal working clamp 5, the upper parts of the anode plate 3 and the cathode plate 4 are respectively connected with the column-shaped scale through the metal working clamp 5 so as to accurately regulate and control the distance between the polar plates, the bottom of the funnel type particle carrier 8 is provided with a hole, the hole diameter is consistent with the size of the aeration stone 9, the opening at the bottom of the funnel type particle carrier 8 is inserted with the aeration stone 9, the aeration stone 9 is hermetically connected with the funnel type particle carrier, the aeration stone 9 is connected with an external aerator 10, the aerator 10 enters an air inlet 11 arranged at the bottom of the cylindrical electrolytic, the device is characterized in that the device is located under an aeration stone, a water draining weir 14 is arranged at the top of the cylindrical electrolytic reactor, a water outlet 15 is arranged in the water draining weir, the outer diameter of the top end of the funnel type particle carrier 8 is consistent with the inner diameter of the cylindrical electrolytic reactor 1, the funnel type particle carrier 8 is connected with the cylindrical electrolytic reactor 1 in a sealing mode, and a plurality of energy dissipation holes are formed in the funnel type particle carrier.
Preferably, the cathode plate uses activated carbon fiber activated by microwave, the anode plate uses titanium-based tin oxide coating electrode,
preferably, the anode is made of a titanium plate as a substrate, the titanium plate is cut into a rectangular plate, the rectangular plate is polished by sand paper, then the rectangular plate is etched by oxalic acid and sodium hydroxide in sequence, then the rectangular plate is soaked in a tin chloride solution filled with alcohol and acid, the solution is kept stand for 12 hours, then the rectangular plate is taken out to be subjected to high-temperature heat treatment, and the soaking-high-temperature heat treatment is repeated to obtain SnO2Coating the anode plate.
Preferably, the energy dissipation holes are uniformly arranged on the funnel-type particle carrier.
Preferably, the thickness of the funnel-type particle carrier is 3-10mm, the energy dissipation holes are arranged in an inclined cone, and the outer surface of the inclined cone on the funnel-type particle carrier is larger than and/or smaller than the pore diameter of the inner surface.
Preferably, the direction of the oblique cone body is consistent with the water flow direction of the spiral water distributor.
Preferably, the aeration stone 9 is directly fixed in a sealing way through a bottom clamping hole of the funnel-type particle carrier 8.
Preferably, the spiral water distributor 13 is in a round cake shape and is arranged right below the aeration stone, and the bottoms of the lower reactors are connected through threads.
Preferably, the top side line of the drainage weir port 14 is about 3-15cm away from the opening of the reactor and is in a bag-shaped curved surface shape, and the central axis of the water outlet 15 is coaxial with the height central line of the weir port.
Preferably, a gas collecting hood is arranged at the top opening of the cylindrical electrolytic reactor.
Preferably, the device can be used as a laboratory test device.
Preferably, the particle diameter of the catalytic particle electrode is smaller than the diameter of the energy dissipation hole.
Preferably, the device is prepared by the following steps:
B1) the anode is made by cutting a titanium plate as a substrate, grinding the titanium plate by abrasive paper, etching by oxalic acid and sodium hydroxide in sequence, soaking the titanium plate in a tin chloride solution filled with alcohol and acid, standing for 12h, taking out the titanium plate for high-temperature heat treatment, and obtaining SnO after repeated soaking-high-temperature heat treatment2Coating the anode plate;
B2) the cathode material adopts activated carbon fiber, and the size of the cathode material is consistent with that of the anode plate; soaking the raw materials in deionized water, performing microwave radiation treatment with the power of 500w, repeatedly cleaning the raw materials with distilled water, and drying the raw materials in a constant-temperature drying box at 105 ℃ for later use;
B3) the catalytic particle electrode is granular active carbon loaded with composite iron oxide and is prepared by a dipping-heat treatment method, and the preparation process comprises the following steps: firstly, soaking activated carbon particles optimized by a 10-100-mesh standard sieve in a ferrous sulfate solution with the concentration of 1mol/L, placing the activated carbon particles in ultrasonic with the power of 50-200W for oscillation for 3 hours, then standing the activated carbon particles for 24 hours, filtering and separating the activated carbon particles, placing the activated carbon particles in a muffle furnace under the protection of nitrogen for heat treatment for 2 hours, wherein the heat treatment temperature is 200-500 ℃, and the heat-treated activated carbon particles are washed by deionized water to obtain a catalytic particle electrode;
B4) fixing the cathode plate and the anode plate manufactured in the step B1 and B2 on two parallel slide rails through a pair of plate clamps respectively, wherein the upper part of each plate clamp is an organic glass clamping plate, the lower part of each plate clamp is tightly buckled at a groove of the I-shaped slide rail, the upper part of each plate clamp is connected with a column-shaped scale through a metal working clamp, the middle scale mark of the column-shaped scale is 0, and the distance between the plates is accurately regulated and controlled;
B5) the size of the outer diameter of the top end of the funnel type particle carrier (8) is consistent with the size of the inner diameter of the cylindrical electrolytic reactor (1), the funnel type particle carrier (8) is hermetically connected with the cylindrical electrolytic reactor (1), and a plurality of energy dissipation holes are formed in the funnel type particle carrier;
B6) the water is delivered by a micro water supply pump, and finally, a water sample is dispersed in the reactor through a spiral water distributor, and the spiral water distributor is connected with the bottom of the reactor through threads.
The three-dimensional funnel type electric Fenton device has the advantages that:
1) the hydrogen peroxide in the three-dimensional electro-Fenton reaction does not need to be added externally, is generated by the automatic reaction of the device, saves the cost, does not need to be regulated and controlled by personnel, and is simple and easy to operate and control.
2) The catalytic particle electrode serves as a three-dimensional electrode, heterogeneous iron oxide provides iron catalytic active species required by the reaction, the iron leaching rate is low, mutual conversion between ferric iron catalytic active species and ferrous iron catalytic active species is realized, so that less precipitate is generated, and meanwhile, the catalytic particle electrode has good stability by using active carbon with a microcrystalline structure as a matrix.
3) The catalytic particle electrode performs rapid and irregular movement between the polar plates under the combined action of spiral water flow and aeration of the spiral water distributor, so that the invalid current and the short-circuit current between the two polar plates are greatly reduced, the surface area of the catalytic particle electrode is fully exerted, pollutants are adsorbed and the three-dimensional electric Fenton reaction is performed simultaneously, and a better treatment effect is achieved.
4) The energy dissipation holes are arranged in an inclined cone, the outer surface of the inclined cone on the funnel type particle carrier is larger than and/or smaller than the aperture of the inner surface, after conversion of the spiral water distributor, water enters in a rotational flow mode, OH generated in the funnel type particle carrier and pollutants are driven to rapidly exchange through the energy dissipation holes in the funnel and fully contact to react, and the reaction efficiency is improved.
5) The metal working clamp, the scale and the polar plate slide rail are utilized to accurately control the distance between the polar plates, and the three-dimensional electric Fenton treatment efficiency can be strengthened in a targeted manner according to the change of water quantity and water quality.
Drawings
FIG. 1 is a schematic diagram of the funnel-type three-dimensional electric Fenton reaction apparatus according to the present example.
FIG. 2 is a front view of a funnel support and its superstructure in this reaction example.
FIG. 3 is a side view of the funnel support and its superstructure in this reaction example.
FIG. 4 is a top view of the funnel support and its superstructure in this reaction example.
FIG. 5 is a graph of TOC degradation rate versus current density.
FIG. 6 is a graph of TOC degradation rate versus fill rate.
FIG. 7 is a graph of TOC degradation rate versus plate spacing.
FIG. 8 is a graph of TOC degradation rate versus pH.
Detailed Description
The present invention is further described in detail below with reference to examples so that those skilled in the art can practice the invention with reference to the description.
It will be understood that terms such as "having," "including," and "comprising," when used herein, do not preclude the presence or addition of one or more other elements or groups thereof.
Example 1
As shown in fig. 1 to 4, the three-dimensional funnel type electric Fenton reaction device comprises a cylindrical electrolytic reactor 1, an electrode plate clamp 2, an anode plate 3, a cathode plate 4, a metal working clamp 5, a cylindrical scale 6, a polar plate slide rail 7, a funnel type particle carrier 8, an aeration stone 9, an aerator 10, an air inlet 11, a micro water delivery pump 12, a spiral water distributor 13, a drainage weir 14 and a water outlet 15.
Wherein the top of the cylindrical electrolytic reactor 1 is open; the funnel type particle carrier 8 is arranged at the middle upper part of the cylindrical electrolytic reactor, the polar plate slide rail 7 is arranged at the top of the funnel type particle carrier, the lower part of the electrode clamping plate 2 is embedded into the polar plate slide rail 7, the polar plate slide rail is an I-shaped slide rail, a power line is connected into the polar plate through the metal working clamp 5, the upper parts of the anode plate 3 and the cathode plate 4 are respectively connected with the column-shaped scale through the metal working clamp 5 so as to accurately regulate and control the distance between the polar plates, the bottom of the funnel type particle carrier 8 is provided with a hole, the hole diameter is consistent with the size of the aeration stone 9, the opening at the bottom of the funnel type particle carrier 8 is inserted with the aeration stone 9, the aeration stone 9 is hermetically connected with the funnel type particle carrier, the aeration stone 9 is connected with an external aerator 10, the aerator 10 enters an air inlet 11 arranged at the bottom of the cylindrical electrolytic, and the funnel-type particle carrier 8 is positioned right below the aeration stone, the top of the cylindrical electrolytic reactor is provided with a water discharge weir 14, a water outlet 15 is arranged in the water discharge weir, the external diameter of the top end of the funnel-type particle carrier 8 is consistent with the size of the internal diameter of the cylindrical electrolytic reactor 1, and the funnel-type particle carrier 8 is hermetically connected with the cylindrical electrolytic reactor 1.
The aeration stone 9 is directly sealed and fixed through a clamping hole at the bottom of the funnel type particle carrier 8, and an air inlet 9 is arranged at the position of the reactor wall corresponding to the pipe orifice.
The spiral water distributor 13 is in a round cake shape and is arranged right below the aeration stone, and the bottom of the lower reactor is connected through threads.
The top side line of the drainage weir crest 14 is about 15cm away from the opening of the reactor and is in a bag-shaped curved surface shape, and the central axis of the water outlet 15 is coaxial with the height central line of the weir crest.
The reaction conditions were set as follows: the current density of the polar plate is 0-12mA/cm2, the initial pH of the solution is =3-7, the filling rate of the catalytic particle electrode is 10-40%, and the aeration intensity is 50L/min.
The flow of treating the wastewater containing the aniline black medicine by using the device of the invention is as follows: conveying water containing target pollutants to a spiral water distributor in a reactor through an external water conveying pump, enabling inlet water to enter the reactor in a rotational flow mode, simultaneously putting catalytic particle electrodes into funnel type particle carriers, inserting cathode and anode plates into electrode clamping plates, positioning the positions of polar plates through a metal working clamp and a column type scale in advance according to the water quality condition of the polluted water, determining the distance between the polar plates, then turning on a direct-current power supply, and turning on a positive power supply and a negative power supplyThe pole power line is connected to the cathode and the anode through the metal working clamp. The catalytic particles in the funnel type particle carrier rapidly move irregularly between two electrodes under the driving of aeration stone aeration, and are polarized into tiny and independent catalytic particle electrodes under the action of current, and under the acidic condition, the cathode part can convert oxygen dissolved in water into H2O2The anode part will strengthen the catalytic particle electrode pair H2O2The catalytic action of the process of decomposing to generate hydroxyl free radical (OH) can efficiently degrade organic pollutants, and the OH can fully contact and react with aniline black powder through energy dissipation holes on particle carriers under the action of a spiral water distributor to achieve an efficient treatment effect, and the treated water body enters a drainage weir port and is discharged through a water outlet.
The principles of operation and use of the present invention are further described below with the selection of aniline black (DDA) as a representative refractory organic contaminant.
Example 2
200mg/L aniline black agent simulation wastewater is input into the device through a miniature water pump, 25% dilute hydrochloric acid and sodium hydroxide are used for regulating the pH value to 3 in advance, then a metal working clamp is used for accurately regulating the distance between the electrode plates to 9cm on a cylindrical scale, an aeration intensity is regulated to 50L/min by an aeration machine, then the filling rates of catalytic particle electrodes are respectively regulated to 30%, see figure 5, the initial organic carbon concentration is measured and recorded as TOC1 before the current is switched on in different groups of experiments, and the current is switched on and the current density is respectively controlled to be 2, 4, 6, 8 and 10mA/cm2After two hours of reaction, the organic carbon concentration is recorded as TOC2, the degradation rate of the organic matter is eta% = (TOC 2-TOC 1)/TOC 1 × 100%, and the experiment shows that: the current density is controlled at 4mA/cm2The degradation effect is best, TOC is reduced from 50.3 to 17.7, the degradation rate is 64.8%, the current density directly reflects the magnitude of input current of the device, if the current supply is insufficient, enough electrons cannot be provided to participate in the oxidative degradation of organic pollutants, but if the current density is too high, the generation of side reactions such as electrolytic water and the like is increased, so that H is hindered2O2The processing rate is reduced.
Example 3
By micro-size200mg/L aniline black drug simulation wastewater is input into the device by a water pump, the pH is adjusted to 3 by 15% dilute hydrochloric acid and sodium hydroxide in advance, then the distance between the plates is accurately adjusted to 7cm by a metal working clamp on a cylindrical scale, the aeration intensity is adjusted to 50L/min by an aeration machine, then the filling rates of catalytic particle electrodes are respectively adjusted to 10%, 20%, 30%, 40% and 50%, the initial organic carbon concentration is measured to be TOC1 under the conditions of different filling rates, the organic carbon concentration is measured to be TOC2 after the current is switched on and the current density is controlled to be 4mA/cm2 to react for two hours, the organic carbon concentration is shown as TOC2 in figure 6, the organic matter degradation rate is eta% = (TOC 2-TOC 1)/TOC 1 multiplied by 100%, and the experiment shows that: after the parameters are optimized in example 2, the degradation effect on organic matters is the best when the filling rate of the catalytic particle electrode is 30%, the TOC is reduced from 50.3 to 16.3, the degradation rate is 67.6%, the efficiency of catalyzing H2O2 to generate OH is improved along with the increase of the dosage of the catalytic particle electrode, and the organic matter degradation rate is not improved by further increasing the dosage of the catalytic particle electrode, probably because the excessive iron-based catalyst can promote H2O2OH is generated by rapid decomposition, while OH generated relatively intensively hinders a contact reaction with a contaminant due to self-trapping, and an excessively high filling ratio inevitably causes a short-circuit current to be generated, thereby lowering the current utilization efficiency of the system.
Example 4
200mg/L of aniline black drug simulation wastewater is input into the device through a miniature water pump, 25% of dilute hydrochloric acid and sodium hydroxide are used for regulating the pH value to 3 in advance, then the distances between the plates are accurately regulated to 3, 4, 6, 7 and 8cm by using metal working clamps on a cylindrical scale, the aeration intensity is regulated to 50L/min by using an aeration machine, see figure 7, then the filling rates of catalytic particle electrodes are respectively regulated to 30%, the initial organic carbon concentration is measured to be TOC1 under different plate distances, the organic carbon concentration is measured to be TOC2 after the current is switched on and the current density is controlled to be 4mA/cm2 and the reaction is carried out for two hours, the organic degradation rate is eta% = (TOC 2-TOC 1)/TOC 1 multiplied by 100%, and the experiment shows that: after the parameters of 2 and 3 are optimized, the degradation effect on organic matters is the best when the distance between the polar plates is adjusted to be 7cm, the TOC is reduced from 50.3 to 14.7, the degradation rate is 70.8%, the selection of the distance between the polar plates is closely related to the magnitude of current density, the current water-flowing path is increased when the distance between the polar plates is too high, the yield of the hydrogen peroxide is reduced, the flowing time of the current between the two polar plates is shortened when the distance between the polar plates is too small, the current density of the solution between the anode and the cathode is indirectly increased, and the reduction of the degradation rate of the organic matters due to the generation of OH in a catalytic mode is.
Example 5
200mg/L of aniline black drug simulated wastewater is input into the device through a miniature water pump, the pH is adjusted to 2, 3, 5, 7 and 9 in advance by 25% of dilute hydrochloric acid and sodium hydroxide, then the distance between electrode plates is accurately adjusted to 7cm on a cylindrical scale by using a metal working clamp, the aeration intensity is adjusted to 50L/min by using an aeration machine, then the filling rate of catalytic particle electrodes is adjusted to be 30%, the initial organic carbon concentration is measured and recorded as TOC1 under different pH values, the initial organic carbon concentration is shown in figure 8, after the current is switched on and the current density is controlled to be 4mA/cm2 to react for two hours, the organic carbon concentration is measured and recorded as TOC2, the organic matter degradation rate is eta% = (TOC 2-TOC 1)/TOC 1 multiplied by 100%, and the experiment shows that: after optimization of parameters of examples 2, 3 and 4, the organic matter degradation rate is highest when the pH value is 3, the TOC is reduced from 50.3 to 14.7, the degradation rate is 70.8%, the pH value is a very critical factor influencing the conversion efficiency of hydrogen peroxide, generally, the reduction of Fe3+ into Fe2+ is hindered under an acidic condition with the pH value being less than 3, and more OH-in the system can promote ineffective decomposition of hydrogen peroxide and capture OH simultaneously with the increase of the pH value to be higher than 3, and the three-dimensional funnel type electric Fenton device still achieves a removal rate of 57.2% at the pH = 7.
While embodiments of the invention have been described above, it is not limited to the applications set forth in the description and the embodiments, which are fully applicable to various fields of endeavor for which the invention may be embodied with additional modifications as would be readily apparent to those skilled in the art, and the invention is therefore not limited to the details given herein and to the embodiments shown and described without departing from the generic concept as defined by the claims and their equivalents.
Claims (10)
1. A three-dimensional funnel type electric Fenton reaction device comprises a cylindrical electrolytic reactor (1), an electrode plate clamp (2), an anode plate (3), a cathode plate (4), a metal working clamp (5), a cylindrical scale (6), a pole plate slide rail (7), a funnel type particle carrier (8), an aeration stone (9), an aerator (10), an air inlet (11), a miniature water delivery pump (12), a spiral water distributor (13), a drainage weir crest (14) and a water outlet (15), wherein the top of the cylindrical electrolytic reactor (1) is open; the funnel type particle carrier (8) is arranged on the middle upper part of the cylindrical electrolytic reactor, the polar plate slide rail (7) is arranged on the top of the funnel type particle carrier, the lower part of the electrode clamping plate (2) is embedded into the polar plate slide rail (7), the polar plate slide rail is an I-shaped slide rail, a power line is connected into a polar plate through the metal working clamp (5), the upper parts of the anode plate (3) and the cathode plate (4) are respectively connected with the column scale (6) through the metal working clamp (5) so as to accurately regulate and control the space between the polar plates, the bottom of the funnel type particle carrier (8) is provided with a hole, the hole diameter is consistent with the size of the aeration stone (9), the hole at the bottom of the funnel type particle carrier (8) is provided with the spigot and socket aeration stone (9), the aeration stone (9) is hermetically connected with the funnel type particle carrier, the aeration stone (9) is connected with the external aeration machine (10), an air inlet (11) is connected with an aeration stone (9) through a closed pipeline, a spiral water distributor (13) is arranged at the bottom of the cylindrical electrolytic reactor (1) and is positioned right below the aeration stone, a water discharge weir (14) is arranged at the top of the cylindrical electrolytic reactor, a water outlet (15) is arranged in the water discharge weir, the external diameter of the top end of the funnel type particle carrier (8) is consistent with the internal diameter of the cylindrical electrolytic reactor (1), the funnel type particle carrier (8) is connected with the cylindrical electrolytic reactor (1) in a sealing manner, and a plurality of energy dissipation holes are formed in the funnel type particle carrier; the preparation process of the catalytic particle electrode comprises the following steps: firstly, soaking activated carbon particles optimized by a 10-100-mesh standard sieve in a ferrous sulfate solution with the concentration of 1mol/L, placing the activated carbon particles in ultrasonic with the power of 50-200W for oscillation for 3 hours, then standing the activated carbon particles for 24 hours, filtering and separating the activated carbon particles, placing the activated carbon particles in a muffle furnace under the protection of nitrogen for heat treatment for 2 hours, wherein the heat treatment temperature is 200-500 ℃, and the heat-treated activated carbon particles are washed by deionized water to obtain the catalytic particle electrode.
2. The device of claim 1, wherein the cathode plate uses microwave activated carbon fibers and the anode plate uses titanium-based tin oxide coated electrodes.
3. The apparatus according to claim 1, wherein the energy dissipating holes are uniformly arranged on the funnel-type particle carrier.
4. The device according to claim 1, wherein the funnel-type particle carrier has a thickness of 3-10mm, and the energy dissipation holes are arranged as inclined cones, and the outer surface of each inclined cone on the funnel-type particle carrier is larger and/or smaller than the pore diameter of the inner surface.
5. The device of claim 1, wherein the direction of the oblique cone is consistent with the water flow direction of the spiral water distributor.
6. The apparatus according to claim 1, characterized in that the aeration stone (9) is directly sealed and fixed by the bottom bayonet hole of the funnel-type particle carrier (8).
7. The device according to claim 1, characterized in that the spiral water distributor (13) is in a round cake shape and is arranged right below the aeration stone, and the bottom of the lower reactor is connected by screw threads.
8. The apparatus of claim 1, wherein the top edge of the drainage weir (14) is about 3-15cm from the reactor opening and is in the shape of a pouch with a central axis of the outlet (15) coaxial with the weir height centerline.
9. The device of claim 1, wherein the device is prepared by:
B1) the anode is made of titanium plate as base body, and is made up by cutting it into rectangular plate, polishing by sand paper, and using oxalic acidEtching with sodium hydroxide, soaking in tin chloride solution filled with alcohol and acid, standing for 12 hr, taking out, performing high temperature heat treatment, and repeating soaking-high temperature heat treatment to obtain SnO2Coating the anode plate;
B2) the cathode material adopts activated carbon fiber, and the size of the cathode material is consistent with that of the anode plate; soaking the raw materials in deionized water, performing microwave radiation treatment with the power of 500w, repeatedly cleaning the raw materials with distilled water, and drying the raw materials in a constant-temperature drying box at 105 ℃ for later use;
B3) the catalytic particle electrode is granular active carbon loaded with composite iron oxide and is prepared by a dipping-heat treatment method, and the preparation process comprises the following steps: firstly, soaking activated carbon particles optimized by a 10-100-mesh standard sieve in a ferrous sulfate solution with the concentration of 1mol/L, placing the activated carbon particles in ultrasonic with the power of 50-200W for oscillation for 3 hours, then standing the activated carbon particles for 24 hours, filtering and separating the activated carbon particles, placing the activated carbon particles in a muffle furnace under the protection of nitrogen for heat treatment for 2 hours, wherein the heat treatment temperature is 200-500 ℃, and the heat-treated activated carbon particles are washed by deionized water to obtain a catalytic particle electrode;
B4) fixing the cathode plate and the anode plate manufactured in the step B1 and B2 on two parallel slide rails through a pair of plate clamps respectively, wherein the upper part of each plate clamp is an organic glass clamping plate, the lower part of each plate clamp is tightly buckled at a groove of the I-shaped slide rail, the upper part of each plate clamp is connected with a column-shaped scale through a metal working clamp, the middle scale mark of the column-shaped scale is 0, and the distance between the plates is accurately regulated and controlled;
B5) the size of the outer diameter of the top end of the funnel type particle carrier (8) is consistent with the size of the inner diameter of the cylindrical electrolytic reactor (1), the funnel type particle carrier (8) is hermetically connected with the cylindrical electrolytic reactor (1), and a plurality of energy dissipation holes are formed in the funnel type particle carrier;
B6) the water is delivered by a micro water supply pump, and finally, a water sample is dispersed in the reactor through a spiral water distributor, and the spiral water distributor is connected with the bottom of the reactor through threads.
10. The method for treating hardly degradable organic wastewater according to any one of claims 1 to 9, wherein:
A. before the water body enters the reactor, after the distance between the polar plates is accurately adjusted in advance through the metal working clamp and the polar plate slide rail, a direct current power supply is switched on, and the catalytic particles generate a polarization effect under the influence of current;
B. the organic wastewater to be treated is sent to a spiral water distributor by a water delivery pump, and the polluted water enters in a rotational flow mode; meanwhile, the surface of the funnel-type particle carrier (8) is provided with energy dissipation holes to accelerate the circulation of the treated sewage in a three-dimensional electric Fenton system, organic pollutants entering the funnel-type particle carrier (8) are uniformly distributed between two polar plates, each particle is divided into a catalytic particle electrode with the characteristics of a cathode and an anode, the circular hole at the lower part of the funnel-type particle carrier is embedded with an aeration stone for aeration driving, oxygen generates oxidation reduction reaction with hydrogen ions in a solution after obtaining electrons at a cathode to generate hydrogen peroxide, and iron-based composite oxides in the catalytic particle electrode catalyze H mainly by the conversion of bivalent iron and trivalent iron in crystal lattices2O2Decomposing to generate a substance with strong oxidizing property, namely hydroxyl free radical, and oxidizing and degrading organic matters in the wastewater after the hydroxyl free radical is fully contacted with the wastewater, wherein ferric ions can be reduced into ferrous ions under the action of a cathode to participate in Fenton reaction, so that continuous Fenton reaction without an additional reagent is realized;
C. and finally, collecting the treated water sample at a water outlet (15).
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111517420A (en) * | 2020-04-17 | 2020-08-11 | 中国科学院金属研究所 | Boron-doped diamond electrode sewage treatment experimental device and operation method thereof |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101844822A (en) * | 2010-05-11 | 2010-09-29 | 沈阳建筑大学 | Three-dimensional electrode/ electro-Fenton reactor |
| CN102101709A (en) * | 2010-11-26 | 2011-06-22 | 方明环保科技(漳州)有限公司 | Electrocoagulation device and method for sewage treatment |
| CN202576054U (en) * | 2012-05-09 | 2012-12-05 | 武汉钢铁(集团)公司 | Three-dimensional electrode reaction device |
| CN103508638A (en) * | 2013-10-15 | 2014-01-15 | 上海纳米技术及应用国家工程研究中心有限公司 | Combined wastewater treatment method through visible light catalysis and immobilized microorganisms and combined reactor |
| CN106745542A (en) * | 2017-03-13 | 2017-05-31 | 盐城工学院 | The photoelectrocatalysis processing system and method for high-salt wastewater |
| CN106986395A (en) * | 2017-04-25 | 2017-07-28 | 上海鼎欣环保工程有限公司 | A kind of water-locator |
| CN209210446U (en) * | 2018-06-13 | 2019-08-06 | 环境保护部南京环境科学研究所 | A kind of novel three-dimensional electrode reaction device |
| CN210457600U (en) * | 2019-08-17 | 2020-05-05 | 湖南科技大学 | Electric Fenton degradation-resistant organic wastewater treatment device |
-
2019
- 2019-08-17 CN CN201910761068.4A patent/CN110589939B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101844822A (en) * | 2010-05-11 | 2010-09-29 | 沈阳建筑大学 | Three-dimensional electrode/ electro-Fenton reactor |
| CN102101709A (en) * | 2010-11-26 | 2011-06-22 | 方明环保科技(漳州)有限公司 | Electrocoagulation device and method for sewage treatment |
| CN202576054U (en) * | 2012-05-09 | 2012-12-05 | 武汉钢铁(集团)公司 | Three-dimensional electrode reaction device |
| CN103508638A (en) * | 2013-10-15 | 2014-01-15 | 上海纳米技术及应用国家工程研究中心有限公司 | Combined wastewater treatment method through visible light catalysis and immobilized microorganisms and combined reactor |
| CN106745542A (en) * | 2017-03-13 | 2017-05-31 | 盐城工学院 | The photoelectrocatalysis processing system and method for high-salt wastewater |
| CN106986395A (en) * | 2017-04-25 | 2017-07-28 | 上海鼎欣环保工程有限公司 | A kind of water-locator |
| CN209210446U (en) * | 2018-06-13 | 2019-08-06 | 环境保护部南京环境科学研究所 | A kind of novel three-dimensional electrode reaction device |
| CN210457600U (en) * | 2019-08-17 | 2020-05-05 | 湖南科技大学 | Electric Fenton degradation-resistant organic wastewater treatment device |
Non-Patent Citations (1)
| Title |
|---|
| 魏毅等: "活性炭载Fe2+三维电极法处理染料废水", 《武汉工程大学学报》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111517420A (en) * | 2020-04-17 | 2020-08-11 | 中国科学院金属研究所 | Boron-doped diamond electrode sewage treatment experimental device and operation method thereof |
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