A highly efficient treatment device for oily wastewater

Abstract

The invention relates to an efficient treatment device for oily sewage applied in the technical field of sewage treatment devices, comprising a magnetic nanoparticle electrode, the magnetic nanoparticle electrode is made of spherical or polygonal ferrite material, and the surface is alternately modified with a catalytic material and a magnetic flocculant, a controller comprises a magnetic field generating module, an ultrasonic generating module and an electrochemical module, which are respectively electrically connected to an ultrasonic transducer, a coil, a reaction chamber body and a foam discharge main pipe, and can apply a magnetic field and a voltage to adjust the electrolysis and magnetic separation process, and introduce the oily sewage into the reaction chamber, under the action of electrolysis, the magnetic nanoparticle electrode dissolves Fe²⁺ ions, reacts with water to generate Fe(OH)₃ colloidal flocculant, adsorbs oil droplets and suspended matter in the water to form flocs, and under the action of a magnetic field, magnetically aggregates and floats to separate, thereby realizing efficient oil-water separation, and hydrogen and oxygen generated by electrolysis are separated and collected for fuel cell power generation, and ultrasonic waves and reverse magnetic fields can regenerate the magnetic nanoparticle electrode.

Description

Technical Field

[0001] The invention relates to a high-efficiency treatment device for oily sewage, and in particular to a high-efficiency treatment device for oily sewage applied in the technical field of sewage treatment devices. Background Art

[0002] Oily wastewater is a common industrial wastewater in the oil extraction, refining, petrochemical, metallurgy, mechanical processing and other industries. The concentrations of pollutants such as oil substances, suspended solids and heavy metals are high. Direct discharge will cause serious pollution to the soil, surface water and groundwater, threatening the ecological environment safety and human health. Traditional oily wastewater treatment processes such as flocculation, flotation, filtration, adsorption, etc. have problems such as low treatment efficiency, large equipment investment, high operating costs, and high risk of secondary pollution. It is difficult to meet the increasingly stringent environmental emission standards and water reuse requirements.

[0003] Chinese invention patent CN114590869B discloses a centrifugal separation treatment device for oily wastewater with IPC classification number C02F. The device stirs the water flow through rotating centrifugal blades and uses centrifugal force to achieve oil-water separation and sand and gravel removal. The device has a simple structure and high separation efficiency, but its processing capacity is limited and it cannot effectively remove fine oil droplets and emulsified oil in the water. The water quality of the effluent is difficult to guarantee. In addition, the precipitated sludge and sand and gravel need to be manually cleaned regularly, which makes operation and management inconvenient.

[0004] Chinese invention patent CN114656069B discloses a safe treatment device for oily wastewater, which uses an automatically cleaning filter to intercept suspended matter and floating oil in the water, and uses a scraper to remove scum on the water surface, thereby improving the purification effect. However, the device has limited filtering accuracy, the filter is easily clogged, the cleaning frequency is high, and it cannot remove soluble pollutants in the water. The scum scraping device has a complex structure, high energy consumption, and is easy to damage.

[0005] The above patented device is mainly used for the removal of suspended matter and free oil in oily wastewater. Although it has achieved oil-water separation to a certain extent, it has poor removal effect on fine emulsified oil droplets, soluble organic matter, etc., and cannot achieve deep treatment. The effluent is difficult to meet the reuse standards. In addition, existing devices generally have problems such as large footprint, high equipment investment, high operating cost, and inconvenient management. It is difficult to meet the needs of on-site treatment and reuse of oily wastewater, and is especially not suitable for use in remote oil fields, offshore platforms and other places lacking fresh water and electricity. Summary of the invention

[0006] In view of the above-mentioned prior art, the technical problem to be solved by the present invention is that although the prior art has achieved oil-water separation to a certain extent, it has poor removal effect on fine emulsified oil droplets, soluble organic matter, etc., cannot achieve deep treatment, and the effluent is difficult to meet the reuse standard. In addition, the existing devices generally have the problems of large footprint, high equipment investment, high operating cost, and inconvenient management.

[0007] In order to solve the above problems, the present invention provides an efficient treatment device for oily wastewater, including a controller and a reaction chamber body, wherein the inner wall of the reaction chamber body is contacted with a plurality of magnetic nanoparticle electrodes, the outer wall of the bottom end of the reaction chamber body is fixedly connected with a plurality of ultrasonic transducers, the outer wall of the bottom end of the reaction chamber body is fixedly connected with a plurality of coils, a plurality of reaction chamber bodies are provided with floating rings, the floating rings are located at the top of the magnetic nanoparticle electrodes, a plurality of foam discharge branch pipes are fixedly connected in the floating rings, the ends of the plurality of foam discharge branch pipes close to each other are fixedly connected with the same foam discharge main pipe, the bottom ends of the plurality of foam discharge branch pipes are all provided with a plurality of through holes, the top of the reaction chamber body is fixedly connected with a gas collection chamber, and the gas collection chamber is fixedly connected with symmetrically arranged A hydrogen separation membrane and an oxygen separation membrane, a hydrogen conduit and an oxygen conduit are fixedly connected at the top of the gas collection chamber and the corresponding positions of the hydrogen separation membrane and the oxygen separation membrane respectively, a fuel cell is fixedly connected to the top of the reaction chamber body, the surface of the magnetic nanoparticle electrode is modified with a magnetic flocculant, the magnetic nanoparticle electrode is made of ferrite, the fuel cell is electrically connected to the controller, the controller includes a magnetic field generating module, an ultrasonic generating module and an electrochemical module, the ultrasonic transducer is electrically connected to the ultrasonic generating module, the coil is electrically connected to the magnetic field generating module, the reaction chamber body and the foam discharge main pipe are electrically connected to the anode and cathode of the electrochemical module respectively, and the electrochemical module is used to apply voltage between the reaction chamber body and the foam discharge main pipe.

[0008] In the above-mentioned oily wastewater high-efficiency treatment device, an electrolytic method is used to generate a high-efficiency flocculant in situ, and an external magnetic field is used to enhance the oil-water-solid separation effect. Specifically, a modified magnetic nanoparticle electrode is arranged in the reactor, oily wastewater is introduced and voltage is applied, and the electrode anode dissolves Fe + , further hydrolyzed to generate Fe(OH) colloidal flocculant. Under acidic conditions, the flocculant carries a positive charge and can attract negatively charged oil droplets and suspended particles in sewage to form loose flocs. Under the action of an external magnetic field and ultrasound, the flocs continue to aggregate and grow, further adsorbing and coating pollutants, and finally quickly separated under the action of gravity and magnetic field. The electrolysis process simultaneously produces hydrogen and oxygen, which are collected and separated for power generation. Stopping the power supply and applying a reverse magnetic field can cause the adsorbed pollutants to detach from the magnetic electrode and be discharged, thus realizing the regeneration and recycling of the electrode.

[0009] As a further improvement of the present application, the magnetic nanoparticle electrode is spherical, and the surface of the magnetic nanoparticle electrode is modified with a catalytic material, and the catalytic material is platinum or palladium.

[0010] As a further improvement of the present application, the catalytic material and the magnetic flocculant are alternately arranged on the surface of the magnetic nanoparticle electrode, the bottom end of the reaction chamber body is a hemispherical structure, and the top end of the reaction chamber body is a cylindrical structure.

[0011] As a further improvement of the present application, the reaction chamber body is made of conductive non-magnetic material, the floating ring is a hollow ring structure, and the outer ends of multiple coils are fixedly connected to the same coil fixing frame.

[0012] As another improvement of the present application, the hydrogen conduit and the oxygen conduit are respectively connected to the fuel cell at one end away from the gas collection chamber, the top of the foam exhaust main pipe passes through the gas collection chamber and extends to the upper side of the gas collection chamber, and the passing part is connected to the external foam collection system.

[0013] As another improved supplement of the present application, the outer end of the foam discharge main pipe is slidably connected to the top of the gas collection chamber, and the two ends of the reaction chamber body are respectively fixedly connected with a liquid inlet pipe and a liquid discharge pipe.

[0014] As another improved supplement of the present application, a slag discharge pipe is fixedly connected to the bottom end of the reaction chamber body, a bracket is fixedly connected to the bottom end of the coil fixing frame, and the floating ring, foam discharge branch pipe and foam discharge main pipe are all made of non-magnetic conductive materials.

[0015] As another improvement of the present application, the number of layers of catalytic material and magnetic flocculant alternately arranged on the surface of the magnetic nanoparticle electrode is 2-10 layers, and the mass ratio of catalytic material to magnetic flocculant in each layer is preferably 1:0.5-1:5. The catalytic material and magnetic flocculant are alternately deposited on the surface of the magnetic nanoparticle electrode by solution impregnation, in-situ reduction, or chemical plating.

[0016] An efficient treatment device for oily wastewater, the use method of which comprises the following steps:

[0017] S1. Mixing the flocculant with the magnetic nanoparticle electrode so that the surface of the magnetic nanoparticle electrode has charges or active groups, which can adsorb pollutants such as oil droplets and suspended matter;

[0018] S2. The water from which large suspended solids in sewage are removed after pretreatment is introduced into the main body of the reaction chamber through a bracket, and a magnetic field and voltage are applied to dissolve the magnetic nanoparticle electrodes and release metal ions Fe²⁺. These metal ions undergo a hydrolysis reaction in the water to generate positively charged colloidal particles, which adsorb negatively charged oil droplets and suspended solids to form floccules.

[0019] S3, adjusting the current to affect the dissolution rate of the magnetic nanoparticle electrode and the amount of metal ions produced, thereby affecting the oil-water separation effect; at the same time, adjusting the magnetic field strength and direction to make the magnetic particles in the magnetic flocculant coating on the magnetic nanoparticle electrode arranged neatly, promoting the aggregation of oil droplets and suspended matter to the magnetic area, and enhancing the flocculation effect;

[0020] S4. Under the action of buoyancy, the flocs float to the floating ring and are continuously discharged through the foam discharge branch pipe and the foam discharge main pipe;

[0021] S5, continue to introduce oily wastewater, and repeat steps S2-S4 until the wastewater treatment is completed;

[0022] S6. Regularly turn on the ultrasonic generating module to generate high-frequency vibration, so that the oil and floccules adsorbed on the surface of the magnetic nanoparticle electrode fall off and are discharged through the slag discharge pipe to regenerate the magnetic nanoparticle electrode; at the same time, apply an external magnetic field to guide the fallen magnetic flocculant to move and concentrate in the direction of the magnetic field to achieve separation from the wastewater, and the separated magnetic flocculant is reused after cleaning;

[0023] S7. The hydrogen and oxygen generated by electrolysis during the collection process are separated by a gas collection chamber, a hydrogen separation membrane and an oxygen separation membrane, and then introduced into a fuel cell to generate electricity, thereby realizing energy recovery and utilization.

[0024] In summary, this application has the following beneficial effects:

[0025] 1. Efficient deep treatment of oily wastewater. The present invention constructs a set of efficient oily wastewater treatment equipment by coupling multiple technologies such as electrolysis, magnetic separation, and ultrasound. Under the action of electrolysis, the magnetic nanoparticle electrode 2 continuously dissolves Fe 2+ Ions react with water to generate Fe(OH)3 colloidal flocculant, which can quickly adsorb oil droplets and suspended matter in water to form flocs. Under the synergistic effect of external magnetic field and ultrasound, the rates of floc aggregation, dehydration, floating and separation are greatly improved. The removal rate of pollutants such as oil, suspended matter and heavy metals in the effluent is high, meeting the discharge and reuse standards of oily wastewater in the petroleum and chemical industries.

[0026] 2. Low equipment investment and low operating cost. Compared with traditional oily wastewater treatment facilities, the device of the present invention is small in size, light in weight, and compact in structure. The magnetic nanoparticle electrode 2 is made of cheap ferrite material, and the electrode has a long service life. By optimizing the electrolyte formula and electrolysis process, Fe 2+ The dissolution rate and current efficiency are significantly improved, and combined with electrolytic gas collection and fuel cell power generation, the operating cost of the device is further reduced, achieving economical and efficient operation.

[0027] 3. The process flow is short and the equipment operation and maintenance are simple. Compared with conventional oily wastewater treatment processes such as flocculation, flotation, filtration, and adsorption, the present invention couples electrolysis and magnetic separation processes, reduces the number of treatment units and equipment, simplifies the process flow, and realizes continuous water inlet, continuous water outlet, and continuous slag discharge. There is no need for manual addition of coagulants. It is fully automatic and intelligently controlled, and one person can manage multiple devices, reducing labor intensity. Ultrasonic and magnetic field regeneration measures ensure the long-term stable operation of the device, and the equipment maintenance cycle can be extended to more than 1 year.

[0028] 4. Environmentally friendly, significant resource and energy recycling. The present invention uses water as electrolyte, and no additional acid, alkali and redox substances are required. The electrolysis process is clean and environmentally friendly. The electrolysis and magnetic separation processes are carried out at room temperature and normal pressure, without heating and pressurization, and no secondary pollutants are discharged. Waste magnetic nanoparticle electrodes can be recycled, and the hydrogen and oxygen produced by electrolysis can be used for power generation and chemical synthesis, achieving waste reduction and resource utilization.

[0029] 5. Wide application scope and strong mobility. The present invention has no special requirements on the source and composition of oily wastewater. It is suitable for on-site treatment and reuse of high-concentration oily wastewater in industries such as oil extraction, oil refining, petrochemicals, metallurgy, and machining. It is especially suitable for remote oil fields, offshore platforms and other places lacking electricity and fresh water, and has significant technical and economic advantages. The present invention can also flexibly adjust the equipment processing scale according to actual needs, realize miniaturization, integration and mobility, and facilitate the factory manufacturing, transportation, installation and on-site commissioning of complete sets of equipment, which greatly broadens the scope of application and promotion prospects. BRIEF DESCRIPTION OF THE DRAWINGS

[0030] Figure 1 This is the overall structure diagram of this application;

[0031] Figure 2 This is an overall exploded view of this application;

[0032] Figure 3 Partial explosion for this application Figure 1 ;

[0033] Figure 4 Partial explosion for this application Figure 2 ;

[0034] Figure 5 This is the front view of the application;

[0035] Figure 6 For this application Figure 5 Middle AA section view;

[0036] Figure 7 This is the appearance structure diagram of this application.

[0037] Description of the numbers in the figure:

[0038] 1. Reaction chamber body; 2. Magnetic nanoparticle electrode; 3. Ultrasonic transducer; 4. Coil; 5. Floating ring; 6. Foam discharge branch pipe; 7. Foam discharge main pipe; 8. Gas collection chamber; 9. Hydrogen separation membrane; 10. Oxygen separation membrane; 11. Hydrogen conduit; 12. Oxygen conduit; 13. Fuel cell; 14. Liquid inlet pipe; 15. Liquid discharge pipe; 16. Slag discharge pipe; 17. Bracket; 18. Coil fixing frame. DETAILED DESCRIPTION

[0039] Three implementation modes of the present application are described in detail below with reference to the accompanying drawings.

[0040] Example 1

[0041] like Figures 1 to 7 As shown, a highly efficient treatment device for oily wastewater comprises a controller and a reaction chamber body 1, wherein the inner wall of the reaction chamber body 1 is provided with a plurality of magnetic nanoparticle electrodes 2 in contact with each other, a plurality of ultrasonic transducers 3 and a plurality of coils 4 are fixedly connected to the outer wall at the bottom end of the reaction chamber body 1, a floating ring 5 is provided inside the reaction chamber body 1, the floating ring 5 is located at the top end of the magnetic nanoparticle electrode 2, a plurality of foam discharge branch pipes 6 are fixedly connected inside the floating ring 5, a same foam discharge main pipe 7 is fixedly connected to one end of the plurality of foam discharge branch pipes 6 close to each other, and a plurality of through holes are provided at the bottom ends of the plurality of foam discharge branch pipes 6.

[0042] A gas collecting chamber 8 is fixedly connected to the top of the reaction chamber body 1, and a symmetrically arranged hydrogen separation membrane 9 and an oxygen separation membrane 10 are fixedly connected inside the gas collecting chamber 8. A hydrogen conduit 11 and an oxygen conduit 12 are fixedly connected to the top of the gas collecting chamber 8 and the corresponding positions of the hydrogen separation membrane 9 and the oxygen separation membrane 10, respectively. A fuel cell 13 is also fixedly connected to the top of the reaction chamber body 1.

[0043] The surface of the magnetic nanoparticle electrode 2 is modified with a magnetic flocculant, and the magnetic nanoparticle electrode 2 is made of ferrite. The fuel cell 13 is electrically connected to the controller, and the controller includes a magnetic field generating module, an ultrasonic generating module and an electrochemical module. The ultrasonic transducer 3 is electrically connected to the ultrasonic generating module, and the coil 4 is electrically connected to the magnetic field generating module. The reaction chamber body 1 and the foam discharge main pipe 7 are electrically connected to the anode and cathode of the electrochemical module respectively, and are used to apply voltage between the reaction chamber body 1 and the foam discharge main pipe 7.

[0044] The reaction chamber body 1 is made of conductive non-magnetic material, such as stainless steel, titanium alloy, etc. The floating ring 5 is a hollow ring structure, and the material can be selected from corrosion-resistant and hydrophobic polymer materials such as polytetrafluoroethylene. The outer ends of multiple coils 4 are fixedly connected to the same coil fixing frame 18, and the coil fixing frame 18 can be made of insulating materials, such as plastic, ceramics, etc.

[0045] The ends of the hydrogen conduit 11 and the oxygen conduit 12 away from the gas collecting chamber 8 are respectively connected to the hydrogen inlet and the oxygen inlet of the fuel cell 13. The top of the foam discharge main pipe 7 penetrates the gas collecting chamber 8 and extends to the upper side of the gas collecting chamber 8, and the penetrating part is connected to the external foam collection system so that the bubbles generated by electrolysis can be discharged in time.

[0046] The outer end of the foam discharge main pipe 7 is connected to the top of the gas collection chamber 8 by sliding, which is convenient for disassembly and maintenance. At the same time, the floating ring 5 floats on the sewage surface, which is convenient for the foam discharge branch pipe 6 to absorb foam. The two ends of the reaction chamber body 1 are respectively fixedly connected with a liquid inlet pipe 14 and a liquid discharge pipe 15 for the inlet and outlet of oily sewage. The bottom end of the reaction chamber body 1 is also fixedly connected with a slag discharge pipe 16 for discharging deposited flocculants and slag.

[0047] The bottom end of the coil fixing frame 18 is fixedly connected with a bracket 17, which can be made of materials with good strength and corrosion resistance such as stainless steel. The floating ring 5, the foam discharge branch pipe 6 and the foam discharge main pipe 7 are all made of non-magnetic conductive materials, such as copper, aluminum, conductive polymers, etc.

[0048] The oily wastewater enters the reaction chamber body 1 through the liquid inlet pipe 14. Under the action of the controller, the coil 4 is energized to generate a magnetic field, the ultrasonic transducer 3 generates ultrasonic waves, and a voltage is applied between the magnetic nanoparticle electrode 2 and the foam discharge main pipe 7. The magnetic nanoparticle electrode 2 electrolyzes and dissolves Fe under the action of the voltage. 2+ Ion, Fe 2+ After the hydrolysis reaction, the ions generate Fe(OH)3 flocculant. Under the synergistic effect of the magnetic field and ultrasound, the magnetic flocculant wraps the oil droplets and suspended matter to form flocs, which gather toward the floating ring 5.

[0049] The flocculants enter the froth discharge branch pipe 6 through the through hole on the froth discharge branch pipe 6, and then are discharged from the reaction chamber main body 1 through the froth discharge main pipe 7 to complete the oil-water separation. The hydrogen and oxygen generated by electrolysis rise to the gas collection chamber 8, and after being separated by the hydrogen separation membrane 9 and the oxygen separation membrane 10, they are transported to the fuel cell 13 by the hydrogen conduit 11 and the oxygen conduit 12 respectively to generate electricity and realize energy recovery and utilization. The treated clear liquid is discharged through the liquid discharge pipe 15, and the flocculant residue is discharged through the residue discharge pipe 16 for collection and treatment.

[0050] The high-efficiency oily wastewater treatment device described in this embodiment can effectively remove pollutants such as oil droplets, suspended matter and heavy metals in oily wastewater through the synergistic effect of magnetic nanoparticle electrodes 2 combined with electrolysis-magnetic separation-ultrasound, thereby achieving deep purification. The arrangement of the foam discharge main pipe 7 and the gas collection chamber 8 can effectively collect the bubbles generated by electrolysis to avoid affecting the oil-water separation effect. The arrangement of the fuel cell 13 can convert the electrolytic gas into electrical energy to achieve energy recovery and utilization, thereby reducing the operating cost of the device. The controller can automatically adjust parameters such as voltage, magnetic field, and ultrasonic wave according to the water quality and treatment requirements of the oily wastewater, thereby achieving optimized control and intelligent operation of the device. The entire device has a compact structure and a reasonable layout, and is easy to maintain and promote. Compared with the traditional oily wastewater treatment process, the device of this embodiment has the advantages of high treatment efficiency, low energy consumption, stable operation, and low secondary pollution. It has broad application prospects in the field of oily wastewater treatment in industries such as petroleum, chemical industry, metallurgy, and machinery manufacturing.

[0051] Example 2

[0052] like Figures 1 to 7 As shown, based on Example 1, this example provides an improved magnetic nanoparticle electrode 2 and a preparation method thereof, wherein the magnetic nanoparticle electrode 2 is spherical or polygonal, with a diameter preferably of 50-500 nm, more preferably of 100-300 nm, and the surface of the magnetic nanoparticle electrode 2 is modified with a catalytic material, and the catalytic material is preferably platinum or palladium.

[0053] The catalytic material and the magnetic flocculant are alternately arranged on the surface of the magnetic nanoparticle electrode 2, and the number of alternating layers is preferably 2-10 layers, and more preferably 4-8 layers. The mass ratio of the catalytic material to the magnetic flocculant in each layer is preferably 1:0.5-1:5, and more preferably 1:1-1:3. The catalytic material and the magnetic flocculant can be alternately deposited on the surface of the magnetic nanoparticle electrode by solution impregnation, in-situ reduction, chemical plating, etc.

[0054] Taking the solution impregnation method as an example, the specific preparation process is as follows:

[0055] 1. Disperse a certain amount of ferroferric oxide nanoparticles in deionized water and disperse them by ultrasonic for 30 minutes to obtain a uniform dispersion;

[0056] 2. Adding cetyltrimethylammonium bromide (CTAB) to the dispersion, stirring for 30 minutes, and standing overnight to obtain surface-modified ferrosoferric oxide nanoparticles;

[0057] 3. Dissolve a certain amount of potassium chloroplatinate in deionized water, add it to the ferroferric oxide nanoparticle dispersion obtained in step 2, and stir for 30 minutes;

[0058] 4. Add ascorbic acid to the mixture obtained in step 3, stir for 30 minutes, react in a 60° C. water bath for 2 hours, cool to room temperature, and centrifuge to obtain platinum-modified ferrosoferric oxide nanoparticles;

[0059] 5. Dissolve a certain amount of magnetic flocculant in deionized water, add it to the product obtained in step 4, stir for 30 minutes, and disperse by ultrasonic for 10 minutes;

[0060] 6. Repeat steps 3-5 until you reach the number of alternating layers you want;

[0061] 7. The product obtained in step 6 is dried under vacuum at 60° C. for 12 hours to obtain a magnetic nanoparticle electrode 2.

[0062] The bottom of the reaction chamber body 1 is a hemispherical structure, and the top is a cylindrical structure. This structural design is conducive to the uniform distribution and movement of the magnetic nanoparticle electrode 2 in the reaction chamber body 1, thereby improving the oil-water separation efficiency.

[0063] After the oily wastewater enters the reaction chamber body 1 through the liquid inlet pipe 14, an oil / water / electrode three-phase interface is formed on the surface of the magnetic nanoparticle electrode 2. The platinum or palladium catalyst can significantly increase the electron transfer rate and hydrogen evolution reaction activity on the electrode surface, promoting the Fe 2+ Ions are generated. At the same time, under the action of magnetic field and ultrasound, the flocculant is cross-linked to form a network structure, which captures oil droplets and suspended particles, generates hydrophobic floccules, and quickly floats to the floating ring 5 to achieve oil-water-solid three-phase separation.

[0064] The bottom of the reaction chamber body 1 with a hemispherical structure is conducive to the sedimentation and collection of suspended matter and flocculants, and the top of the cylindrical structure is conducive to the rising and discharge of bubbles and scum, further enhancing the oil-water separation effect.

[0065] The improved scheme of the magnetic nanoparticle electrode 2 described in this embodiment, through the alternating modification of catalysts and flocculants, not only improves the electrocatalytic activity of the electrode surface, but also enhances the capture and flocculation ability of oil droplets and suspended matter, which can improve the treatment efficiency of oily wastewater and the effluent water quality.

[0066] Compared with ordinary magnetic material electrodes, the multi-layer alternating modified structure increases the electrode specific surface area and active sites, while preventing the flocculant from falling off, improving the service life and stability of the electrode. The optimized design of the reaction chamber main structure further enhances the oil-water separation effect, reduces energy consumption and operating costs, and the entire electrode preparation process is simple, the raw materials are easily available, and it is suitable for large-scale production and application.

[0067] The magnetic nanoparticle electrode 2 of this embodiment can be used in the high-efficiency oily wastewater treatment device described in Example 1, and can also be used in other types of electrolysis-magnetic separation coupling devices, and has broad application prospects in the fields of industrial wastewater treatment, contaminated site remediation, and deep purification of drinking water.

[0068] Example 3

[0069] like Figures 1 to 7 As shown, this embodiment provides a method for using the oily wastewater efficient treatment device described in Embodiments 1 and 2, comprising the following steps:

[0070] S1. Mix the flocculant with the magnetic nanoparticle electrode 2 so that the surface of the magnetic nanoparticle electrode 2 has an electric charge or active groups, which can adsorb pollutants such as oil droplets and suspended matter. The flocculant can be a cationic or amphoteric polymer flocculant such as polyacrylamide and polydiallyldimethylammonium chloride. The added amount is 0.01-0.1% of the sewage volume. Mix it evenly with the magnetic nanoparticle electrode 2 and let it stand for 10-30 minutes to allow the flocculant to be fully adsorbed on the electrode surface.

[0071] S2, the water from which large suspended solids in the sewage are removed after pretreatment is introduced into the reaction chamber body 1 through the bracket 17, and a magnetic field and voltage are applied, the magnetic field strength is 0.5-2.0 T, and the voltage is 5-20 V. Under the action of the magnetic field and voltage, the magnetic nanoparticle electrode 2 undergoes electrochemical dissolution, releasing Fe 2+ Ion, Fe 2+ The ions are hydrolyzed in water to form Fe(OH)3 colloidal particles, which are positively charged and can adsorb negatively charged oil droplets and suspended matter in the water to form flocs.

[0072] S3, adjust the electrolysis current density to 10-100 mA / cm2, affecting the dissolution rate of the magnetic nanoparticle electrode 2 and Fe 2+ The amount of ions generated affects the oil-water separation effect. At the same time, the current size and direction of the coil 4 are adjusted to make the magnetic particles in the magnetic flocculant coating on the electrode surface align and orient in the external magnetic field to form a hydrophobic magnetic area, which promotes the aggregation of oil droplets and suspended matter to the magnetic area and enhances the flocculation effect.

[0073] S4. Continue to introduce oily wastewater. Under the action of buoyancy, the flocs float to the floating ring 5, and are continuously discharged through the foam discharge branch pipe 6 and the foam discharge main pipe 7. The diameter of the foam discharge branch pipe 6 is 5-20 mm, and the diameter of the foam discharge main pipe 7 is 20-50 mm.

[0074] S5. Continue to introduce oily wastewater and repeat steps S2-S4 until the wastewater treatment is completed.

[0075] S6. Turn on the ultrasonic generating module every 2-24 hours, apply ultrasonic waves with a frequency of 20-100kHz and a power of 50-500 W to the magnetic nanoparticle electrode 2 for 10-60 minutes, so that the oil and flocs adsorbed on the electrode surface fall off and are discharged through the slag discharge pipe 16 to regenerate the electrode. At the same time, apply a reverse magnetic field to guide the detached magnetic flocculant to move and concentrate in the direction of the slag discharge pipe 16 to achieve separation from the wastewater. The separated magnetic flocculant is washed with tap water or compressed air and then reused.

[0076] S7. The hydrogen and oxygen generated by electrolysis during the collection process are separated by the gas collection chamber 8, the hydrophobic hydrogen separation membrane 9 and the oxygen separation membrane 10, and then introduced into the proton exchange membrane fuel cell 13 to generate electricity, which can power the device or generate electricity in grid connection, realize energy recovery and utilization, and reduce the operating cost of the device.

[0077] When in use, the flocculant is mixed with the magnetic nanoparticle electrode 2 so that the surface of the magnetic nanoparticle electrode 2 carries an electric charge or active groups, which can adsorb pollutants such as oil droplets and suspended matter. The water from which large suspended matter in the sewage is removed after pretreatment is introduced through the bracket 17, and then the foam discharge main pipe 7 and the reaction chamber body 1 are energized through the controller. When the current passes through the solution containing the oil-water mixture, the magnetic nanoparticle electrode 2 as the anode will dissolve and release metal ions Fe²⁺. These metal ions undergo a hydrolysis reaction in the water to generate positively charged colloidal particles. These colloidal particles can adsorb negatively charged oil droplets and suspended matter to form larger flocs. By regulating the current, the dissolution rate of the electrode and the amount of metal ions generated can be affected, thereby affecting the effect of oil-water separation.

[0078] The electrochemically generated froth is gathered into the froth discharge main pipe 7 through a plurality of froth discharge branch pipes 6 and discharged through the froth discharge main pipe 7 .

[0079] At the same time, a magnetic field is generated by multiple coils 4, so that the magnetic flocculant coating on the magnetic nanoparticle electrode 2 is arranged neatly under the action of the external magnetic field, thereby promoting the aggregation of oil droplets and suspended matter to these magnetic areas. By changing the intensity and direction of the magnetic field, the flocculation effect can be further enhanced, making it easier for oil droplets and suspended matter to form larger agglomerates, which is convenient for subsequent separation.

[0080] The controller automatically adjusts the magnetic field and current parameters according to the water quality parameters.

[0081] The gas generated by electrolysis is collected by the gas collection chamber 8 and separated by the hydrogen separation membrane 9 and the oxygen separation membrane 10 , and then converted into electrical energy by the fuel cell 13 .

[0082] The magnetic nanoparticle electrodes 2 are cleaned periodically by ultrasound and magnetic field reversal mechanisms.

[0083] After flocculation is completed, the magnetic flocculant is guided to move in the direction of the magnetic field by applying an external magnetic field. The magnetic flocculant will quickly concentrate in the area with a stronger magnetic field, thereby achieving effective separation from the wastewater. The separated magnetic flocculant is discharged from the slag discharge pipe 16 and can be reused after cleaning, which helps to reduce costs and improve treatment efficiency.

[0084] During use, the cleaned magnetic flocculant is continuously added to the wastewater containing pollutants.

[0085] The method of this embodiment fully utilizes the structural advantages of the device of Example 1 and the performance advantages of the electrodes of Example 2, and achieves efficient and deep treatment of oily wastewater by finely controlling the electrolysis-magnetic separation-ultrasonic synergistic process.

[0086] During the treatment process, Fe 2+The amount of ion dissolution is controllable, and the collision probability of the generated Fe(OH)3 colloidal flocculant with oil droplets and suspended matter in water is increased, which accelerates the flocculation rate and oil-water separation efficiency. The external magnetic field induces the magnetic flocculant coating on the electrode surface to form an ordered hydrophobic area, which further strengthens the magnetic aggregation effect of oil droplets and flocs. Regular ultrasonic cleaning and reverse magnetic field regeneration can effectively solve the problems of electrode surface contamination and passivation, ensuring long-term stable operation of the device.

[0087] Compared with the traditional oily wastewater treatment process, the method of this embodiment has the characteristics of low equipment investment, small footprint, simple operation and management, and good effluent quality. It is particularly suitable for on-site treatment and reuse of small oily wastewater in the petroleum, chemical and other industries. Combined with fuel cell power generation, the device can achieve self-sufficient operation, and its advantages are more prominent in remote oil fields, offshore platforms and other places where there is a lack of electricity.

[0088] In view of current practical needs, the above-mentioned implementation mode adopted in this application is not limited to the scope of protection. Various changes made within the knowledge scope of technical personnel in this field without departing from the concept of this application still fall within the scope of protection of the present invention.

Claims

1. An efficient treatment device for oily wastewater, characterized in that: The invention comprises a controller and a reaction chamber body (1), wherein the inner wall of the reaction chamber body (1) is provided with a plurality of magnetic nanoparticle electrodes (2), the outer wall of the bottom end of the reaction chamber body (1) is fixedly connected with a plurality of ultrasonic transducers (3), the outer wall of the bottom end of the reaction chamber body (1) is fixedly connected with a plurality of coils (4), a plurality of floating rings (5) are provided inside the reaction chamber body (1), the floating rings (5) are located at the top end of the magnetic nanoparticle electrodes (2), a plurality of foam discharge branch pipes (6) are fixedly connected inside the floating rings (5), the ends of the plurality of foam discharge branch pipes (6) close to each other are fixedly connected with the same foam discharge main pipe (7), the bottom ends of the plurality of foam discharge branch pipes (6) are all provided with a plurality of through holes, the top end of the reaction chamber body (1) is fixedly connected with a gas collection chamber (8), the gas collection chamber (8) is fixedly connected with symmetrically arranged hydrogen separation membranes (9) and oxygen separation membranes (10), and the gas collection chamber (8) is fixedly connected with the symmetrically arranged hydrogen separation membranes (9) and oxygen separation membranes (11). 10), a hydrogen conduit (11) and an oxygen conduit (12) are fixedly connected at the top of the gas collection chamber (8) and the corresponding positions of the hydrogen separation membrane (9) and the oxygen separation membrane (10), respectively; a fuel cell (13) is fixedly connected at the top of the reaction chamber body (1); the surface of the magnetic nanoparticle electrode (2) is modified with a magnetic flocculant; the magnetic nanoparticle electrode (2) is made of ferrite; the fuel cell (13) is electrically connected to a controller; the controller comprises a magnetic field generating module, an ultrasonic generating module and an electrochemical module; the ultrasonic transducer (3) is electrically connected to the ultrasonic generating module; the coil (4) is electrically connected to the magnetic field generating module; the reaction chamber body (1) and the foam discharge main pipe (7) are electrically connected to the anode and cathode of the electrochemical module, respectively; the electrochemical module is used to apply a voltage between the reaction chamber body (1) and the foam discharge main pipe (7).

2. The device for efficiently treating oily wastewater according to claim 1 is characterized in that: The magnetic nanoparticle electrode (2) is spherical, and the surface of the magnetic nanoparticle electrode (2) is modified with a catalytic material, wherein the catalytic material is platinum or palladium.

3. The device for efficiently treating oily wastewater according to claim 2 is characterized in that: The catalytic material and the magnetic flocculant are alternately arranged on the surface of the magnetic nanoparticle electrode (2); the bottom end of the reaction chamber body (1) is a hemispherical structure; and the top end of the reaction chamber body (1) is a cylindrical structure.

4. The device for efficiently treating oily wastewater according to claim 1 is characterized in that: The reaction chamber body (1) is made of a conductive non-magnetic material, the floating ring (5) is a hollow ring structure, and the outer ends of the plurality of coils (4) are fixedly connected to the same coil fixing frame (18).

5. The device for efficiently treating oily wastewater according to claim 1 is characterized in that: The ends of the hydrogen conduit (11) and the oxygen conduit (12) away from the gas collection chamber (8) are respectively connected to the fuel cell (13); the top end of the foam discharge main pipe (7) penetrates the gas collection chamber (8) and extends to the upper side of the gas collection chamber (8), and the penetrated portion is connected to an external foam collection system.

6. The device for efficiently treating oily wastewater according to claim 1 is characterized in that: The outer end of the foam discharge main pipe (7) is slidably connected to the top of the gas collection chamber (8), and the two ends of the reaction chamber body (1) are respectively fixedly connected with a liquid inlet pipe (14) and a liquid discharge pipe (15).

7. The device for efficiently treating oily wastewater according to claim 4 is characterized in that: The bottom end of the reaction chamber body (1) is fixedly connected to a slag discharge pipe (16), the bottom end of the coil fixing frame (18) is fixedly connected to a bracket (17), and the floating ring (5), the foam discharge branch pipe (6) and the foam discharge main pipe (7) are all made of non-magnetic conductive materials.

8. The device for efficiently treating oily wastewater according to claim 2 is characterized in that: The number of layers of the catalytic material and the magnetic flocculant alternately arranged on the surface of the magnetic nanoparticle electrode (2) is 2-10, the mass ratio of the catalytic material to the magnetic flocculant in each layer is 1:0.5-1:5, and the catalytic material and the magnetic flocculant are alternately deposited on the surface of the magnetic nanoparticle electrode by any one of the three methods of solution impregnation, in-situ reduction or chemical plating.

9. The device for efficiently treating oily wastewater according to claim 7 is characterized in that: The method of use includes the following steps: S1, mixing a flocculant with a magnetic nanoparticle electrode (2) so that the surface of the magnetic nanoparticle electrode (2) has an electric charge or an active group, which can adsorb pollutants such as oil droplets and suspended matter; S2. The water from which large suspended solids in the sewage are removed after pretreatment is introduced into the reaction chamber body (1) through the bracket (17), and a magnetic field and voltage are applied to dissolve the magnetic nanoparticle electrode (2) to release metal ions Fe²⁺. These metal ions undergo a hydrolysis reaction in the water to generate positively charged colloidal particles, which adsorb negatively charged oil droplets and suspended solids to form floccules; S3, adjusting the current to affect the dissolution rate of the magnetic nanoparticle electrode (2) and the amount of metal ions produced, thereby affecting the oil-water separation effect; at the same time, adjusting the magnetic field strength and direction to make the magnetic particles in the magnetic flocculant coating on the magnetic nanoparticle electrode (2) arranged neatly, promoting the aggregation of oil droplets and suspended matter to the magnetic area, and enhancing the flocculation effect; S4, under the action of buoyancy, the flocs float up to the floating ring (5), and are continuously discharged through the froth discharge branch pipe (6) and the froth discharge main pipe (7); S5, continue to introduce oily wastewater, and repeat steps S2-S4 until the wastewater treatment is completed; S6, regularly turning on the ultrasonic generating module to generate high-frequency vibration, so that the oil and flocculent adsorbed on the surface of the magnetic nanoparticle electrode (2) fall off and are discharged through the slag discharge pipe (16), thereby regenerating the magnetic nanoparticle electrode; at the same time, applying an external magnetic field to guide the detached magnetic flocculant to move and concentrate in the direction of the magnetic field, thereby achieving separation from the wastewater, and the separated magnetic flocculant is reused after being cleaned; S7. The hydrogen and oxygen generated by electrolysis during the collection and treatment process are separated by a gas collection chamber (8), a hydrogen separation membrane (9) and an oxygen separation membrane (10), and then introduced into a fuel cell (13) to generate electricity, thereby realizing energy recovery and utilization.

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