CN104003481B - A kind of electrofiltration plate and the application in high concentrated organic wastewater thereof - Google Patents
A kind of electrofiltration plate and the application in high concentrated organic wastewater thereof Download PDFInfo
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Abstract
The present invention relates to a kind of electrofiltration plate, it is made anode and cathode integration filter plate by anode electrocatalysis material, cathode electrocatalyst material, micro-electrolysis material, or is made plate-shaped anode filter plate or negative electrode filter plate by anode electrocatalysis material or cathode electrocatalyst material, micro-electrolysis material, conductive material；When electrofiltration plate is applied to high concentrated organic wastewater process, being combined novel parallel board-like ultrasonic reactor, synergism is notable；Strong oxidizing property OH of the reactions such as electro-catalysis that in waste water, organic compound is caused by electrofiltration plate, light electrolysis, electricity flocculation and ultrasonic generation is degraded, and becomes micromolecular compound, improves wastewater biodegradability；Oxide on electrofiltration plate can be effectively cleaned in the mechanical shearing effect of the most ultrasonic generation, overcomes the shortcoming that tradition electrocatalysis material easy in inactivation passivation, micro-electrolysis material easily harden, it is ensured that electrochemical reaction activity, significantly improves treatment effeciency.
Description
Technical field
The present invention relates to a kind of electrofiltration plate and the application in processing high concentrated organic wastewater thereof, belong to pollutant effluents process field.
Background technology
Fast development along with China's chemical industry, various novel chemical products are applied to all trades and professions, particularly coking, chemical industry, electroplate, in the heavily contaminated industry such as printing and dyeing, also the most serious problem of environmental pollution is brought while improving product quality, quality, it is mainly manifested in: Organic Pollutants in Wastewater concentration height, Stability Analysis of Structures, biochemical are poor, common process is difficult to qualified discharge, and processing cost is high, and the target realizing energy-saving and emission-reduction to enterprise brings enormous pressure.Organic wastewater particularly high salt high concentrated organic wastewater processes, the difficult problem that always numerous domestic environmental worker and administration section pay close attention to.
Tradition light electrolysis equipment major part is fixed bed, and filler typically uses ferrum carbon mix, is characterized in simple in construction, good fluidity, but still suffer from some practicality problems: mixed fillers is overlapped to be overstock, and easily causes bed body and hardens, form short circuit and dead band, make treatment effeciency reduce；The iron of ferrum dissolution in acid condition is big, supplements iron filings labor intensity big.Larger molecular organics in waste water can be converted into micromolecular compound by its cavitation effect, mechanical shearing and tiny flocculation effect by supersound process, thus improves wastewater biodegradability.But individually applications of ultrasound is when high concentrated organic wastewater processes, often cannot obtain gratifying effect, and energy consumption is higher, thus limit the industrial applications of this treatment technology.
Summary of the invention
When the invention aims to solve the actual application of existing light electrolysis equipment, filler easily hardens, inactivation, service life is short, change the shortcoming that filler labor intensity is big, provide a kind of electrofiltration plate, it is by anode electrocatalysis material, cathode electrocatalyst material, micro-electrolysis material makes tabular anode and cathode integration filter plate, or by anode electrocatalysis material or cathode electrocatalyst material, micro-electrolysis material, conductive material makes plate-shaped anode filter plate or negative electrode filter plate, anode electrocatalysis material and/or cathode electrocatalyst material are arranged at micro-electrolysis stuffing both sides or are mixed in micro-electrolysis stuffing；When electrocatalysis material is mixed in micro-electrolysis material, being pressed into tabular, the mixing quality of electrocatalysis material and micro-electrolysis material is than for 1:1 ~ 1:3；During preparation anode and cathode integration electrofiltration plate, the mixing quality of anode electrocatalysis material and cathode electrocatalyst material ratio is for 2:1 ~ 1:1.
Described cathode electrocatalyst material is titanium, rustless steel or graphite, anode electrocatalysis material is Ti-Ni alloy, the violent alloy of titanium or titanium magnesium alloy, electrocatalysis material is perforated plate-like or the granule formed by porous plate shearing-crushing, on porous plate, the aperture in hole is 30 ~ 200 mesh, the broken particle length formed is 5 ~ 15mm, and width is 3 ~ 6mm.
Described micro-electrolysis material is mixed by ferrum-carbon or aluminum-carbon, and its mixed volume is than for 0.8:1 ~ 1.2:1；Light electrolysis mixed fillers various shapes, has that granule is spherical, porous cylindrical or a unsetting granule；Micro-electrolysis stuffing particle size range is 18 ~ 100 mesh, adds or the cycle of replacing filler is 1 ~ March during use；Micro-electrolysis material can be properly added copper scale or platinum bits (particle diameter is 18 ~ 100 mesh) that percent by volume is 0.1% ~ 0.3%, for increasing the potential difference of filler, adjuvant can also be added thus be prevented effectively from filler and the phenomenon that hardens occurs, it is simultaneously also beneficial to solid-liquid be fully contacted, promote treatment effect, adjuvant selects polyethylene or polypropylene hollow baton round, a diameter of 5 ~ 38mm of hollow plastic ball.
Described conductive material is a diameter of 0.8 ~ 6.0 mm of copper cash or nickel wire, copper cash or nickel wire, S-shaped, Z-shaped is distributed in micro-electrolysis material, is distributed if conductive material is more than one in river font；Depending on conductor length of material is according to electrofiltration plate size, it is ensured that electrofiltration plate is energized without dead angle.
Electrofiltration plate thickness of the present invention is 10 ~ 50 mm, and electrofiltration plate can be provided with bracing frame, and bracing frame is made up of politef or polyethers ether resin of copper (PEEK resin) material, is wrapped in electrofiltration plate surrounding.
nullThe present invention another object is that and is used for processing in high concentrated organic wastewater device by electrofiltration plate，This device includes reactor 2、Power supply 3、Time switch 4、The electrofiltration plate of more than two pieces、Air pump 9、Ultrasonic transducer 11、Supersonic generator 12、Aeration tube 13，Electrofiltration plate is arranged in reactor 2 by draw-in groove，Electrofiltration plate is connected with power supply 3 by time switch 4，Aeration tube 13 is arranged on bottom reactor 2，Aeration tube 13 is connected with air pump 9 by effusion meter 7，Water inlet and outlet it is provided with on reactor 2，Two or more ultrasonic transducer 11 is symmetrically mounted on outside two parallel with electrofiltration plate reactor wall，Electrofiltration plate is vertical with ultrasonic propagation direction，Ultrasonic transducer is connected with supersonic generator，Electrofiltration interplate spacing is the distance between 40 ~ 80 mm(dissimilar electrofiltration plate)；
Wherein the set-up mode of electrofiltration plate is as follows:
A, monolithic anode filter plate and monolithic negative electrode filter plate use the over-over mode of " sun-male-female-the moon (sun-male-female, male-female-yin, yang-the moon) " to be distributed in reactor；When anode filter plate quantity is more than negative electrode filter plate, the oxidation reaction occurred in reactor is occupied an leading position, at this moment high to process reductive organic matter concentration waste water；When negative electrode filter plate quantity is more than anode filter plate, the reduction reaction occurred in reactor is occupied an leading position, at this moment high to process oxidisability organic concentration waste water；
B, by 2 ~ 4 pieces series connection anode filter plates and 2 ~ 4 pieces of series cathode filter plates be distributed in reactor with the over-over mode of " sun-male-female-the moon (sun-male-female, male-female-yin, yang-the moon) ", again series connection anode filter plate and series cathode filter plate are coupled together after setting；
C, when in reactor electrofiltration plate be 1 ~ 4 piece of series connection anode filter plate or 1 ~ 4 piece of series cathode filter plate with the combination of more than 1 piece anode and cathode integration filter plate time, series connection anode filter plate or series cathode filter plate filter plate integrated with anode and cathode are distributed in reactor with " male/female-integration-integration-male/female-integration (integrated-male/female-integrated, male/female-integrated) " over-over mode；
D, when in reactor, electrofiltration plate is 1 ~ 4 piece of series connection anode filter plate, 1 ~ 4 piece of series cathode filter plate and the combination of more than 1 piece anode and cathode integration filter plate, the electrofiltration plate of three types is alternately distributed in reactor；
E, when in reactor electrofiltration plate be the anode and cathode integration filter plate of more than 1 piece, itself and power sources in series.
At the ultrasonic transducer of stainless steel reactor opposite welding equal number, form parallel plate type ultrasonic reactor, and be connected with supersonic generator, it is ensured that operating power and frequency adapt.Supersonic generator operating frequency and power bracket are respectively 17 ~ 68 kHz and 300 ~ 2700 W.
Ultrasonic transducer on described reactor outer wall is regular shape such as hexagon, circle or Triangle-Profile, spacing distance between two ultrasonic transducers is 200 ~ 400 mm, the corresponding ultrasonic transducer on reactor outer wall is symmetrically distributed, and the spacing installed between two outer walls of ultrasonic transducer is 160 ~ 200 mm；Inside reactor is provided with draw-in groove, makes electrofiltration plate distribution mode vertical with ultrasonic propagation direction.
The electrofiltration plate fixed by gripper shoe is put into reactor draw-in groove fix, then electrofiltration plate is connected with regulated power supply, pulse voltage, DC voltage or alternating voltage can be used, voltage range is 0.1 ~ 8.0V, electrofiltration plate spacing is 40 ~ 80 mm, after switching on power, electrofiltration plate will occur the series reaction such as electro-catalysis, light electrolysis, electricity flocculation.Reactor bottom is provided with aeration tube, and aeration rate is 70 ~ 200 L h-1。
During use, high concentrated organic wastewater is in water inlet puts into reactor, the water surface slightly higher than ultrasonic transducer height also covers electrofiltration plate, open the aerator of reactor bottom, open supersonic generator and on and off switch, high concentrated organic wastewater, after supersound process 20 ~ 120 min worked in coordination with by electrofiltration plate, enters next flow process by outlet and carries out biochemical treatment further.
In high concentrated organic wastewater, Organic substance is mainly degraded by following two mode: 1. electrofiltration plate effect；The redox reaction that the oxidation reaction of the anode surface generation of anode filter plate surface or anode and cathode integration filter plate and the reduction reaction of the cathode surface generation of negative electrode filter plate or anode and cathode integration filter plate and micro-electrolysis stuffing are occurred after forming galvanic element, macromolecular organic compound can be effectively degraded into micromolecular compound by these redox reaction, the product that anode electrocatalysis material and micro-electrolysis material anode generate owing to there is galvano-cautery simultaneously also can occur redox reaction with the pollutant in waste water further, produce absorption, flocculation sediment etc., realize removing further the purpose of pollutant.2. ul-trasonic irradiation；Ultrasonic cavitation effect produces the OH of strong oxidizing property, part hardly degraded organic substance oxidative degradation in waste water can be become degradable or small organic molecule.And, ultrasound wave has cleaning action, can effectively remove electrode surface oxide, prevents electrocatalysis material inactivation passivation, micro-electrolysis stuffing from hardening, thus ensureing service life and the treatment effeciency of electrofiltration plate.Additionally, reactor bottom arranges aerator, while providing a large amount of cavitation nucleus strengthening supersound process efficiency for ultrasound cavitation effect, is also effectively improved the potential difference between micro-electrolysis stuffing, increase galvanic interaction, accelerate ferrum/aluminum bits surface reactant and liquid material exchange speed.Water outlet biodegradability after being jointly processed by significantly improves, effectively reduce subsequent biochemical intractability, and due to when electrofiltration plate uses applied voltage low, energy consumption is little, and treatment effect is substantially better than tradition light electrolysis equipment, therefore electrofiltration plate has using value and prospect in terms of high concentrated organic wastewater process very much.
The present invention is as follows relative to the advantage of prior art and technique effect:
Strong oxidizing property OH that the reactions such as electro-catalysis that 1, Coal Gas Washing Cycling Water organic compound is caused by electrofiltration plate, light electrolysis, electricity flocculation and ultrasonic cavitation effect produce is degraded, and becomes micromolecular compound, makes the biodegradability of organic wastewater be improved；
2, oxide on electrofiltration plate can be effectively cleaned in the mechanical shearing effect that ultrasound wave produces, thus overcomes the shortcoming that tradition electrocatalysis material easy in inactivation is passivated, micro-electrolysis material easily hardens, it is ensured that electrochemical reaction activity, is effectively improved treatment effeciency；
When 3, electrofiltration plate is applied to high concentrated organic wastewater process, connected mode is various, and the formal distribution totally so replaced with male-female is combined novel parallel board-like ultrasonic reactor simultaneously, and synergism is notable；
4, applied voltage is low, less energy consumption, is advantageously implemented the purpose of energy-saving and emission-reduction；
The inventive method is workable, and technological design is simple, with low cost, can efficiently reduce content of organics in waste water, improve wastewater biodegradability, realize qualified discharge for subsequent treatment or recycling lays good basis, in high concentrated organic wastewater processes, there is applications well prospect.
Accompanying drawing explanation
Fig. 1 is negative electrode electrofiltration plate structure schematic diagram of the present invention, and conductor material is distributed as a example by S-shaped, and wherein a is that electrocatalysis material is arranged at micro-electrolysis stuffing both sides；B is that electrocatalysis material is mixed in micro-electrolysis stuffing；
Fig. 2 is anode electrofiltration plate structure schematic diagram of the present invention, and conductor material is distributed as a example by S-shaped, and wherein a is that electrocatalysis material is arranged at micro-electrolysis stuffing both sides；B is that electrocatalysis material is mixed in micro-electrolysis stuffing；
Fig. 3 is anode and cathode integration electrofiltration plate structure schematic diagram of the present invention, and wherein a is that electrocatalysis material is arranged at micro-electrolysis stuffing both sides；B is that electrocatalysis material is mixed in micro-electrolysis stuffing；
Fig. 4 is that the present invention processes high concentrated organic wastewater apparatus structure schematic diagram；
Fig. 5 is the structural representation processing high concentrated organic wastewater device that the present invention uses anode and cathode integration filter plate；
In figure: 1-water inlet；2-reactor body；3-power supply；4-time switch；5-negative electrode filter plate；6-anode filter plate；7-gas flowmeter；8-valve；9-air pump；10-outlet；11-ultrasonic transducer；12-supersonic generator；13-aeration tube；14-anode electrocatalysis material；15-cathode electrocatalyst material；16-micro-electrolysis material；17-conductive material, 18-anode and cathode integration filter plate.
Detailed description of the invention
With embodiment, the present invention is described in further detail below in conjunction with the accompanying drawings, but protection scope of the present invention is not limited to described content.
Embodiment 1: this electrofiltration plate is negative electrode filter plate, anode filter plate, negative electrode electrofiltration plate includes cathode electrocatalyst material, micro-electrolysis material and conductor material, anode electrofiltration plate includes anode electrocatalysis material, micro-electrolysis material and conductor material, wherein cathode electrocatalyst material is titanium, anode electrocatalysis material is Ti-Ni alloy plate, structure is perforated plate-like, and on porous plate, the aperture in hole is 30 mesh；Electrofiltration plate thickness is 10 mm, and electrocatalysis material is pressed into tabular and is distributed in micro-electrolysis material both sides；Micro-electrolysis material is mixed according to volume ratio 0.8:1 ratio by aluminum-carbon, it is spherical that it is shaped as granule, particle size range is 18 mesh, micro-electrolysis material increases the copper scale (particle diameter is 18 mesh) that volume ratio is 0.1% and increases the potential difference of filler, add adjuvant polyethylene hollow plastic ball, a diameter of 5 mm of hollow ball；Conductor material selection nickel wire, specification is 0.8 mm, S-shaped is distributed in micro-electrolysis stuffing (see Fig. 1 a, Fig. 2 a).
nullIt is applied to negative electrode filter plate in the present embodiment and anode filter plate process in high concentrated organic wastewater device，This device includes reactor 2、Power supply 3、Time switch 4、Negative electrode filter plate 5、Anode filter plate 6、Air pump 9、Ultrasonic transducer 11，Supersonic generator 12、Aeration tube 13，Negative electrode filter plate 5 and anode filter plate 6 are arranged in reactor 2 by draw-in groove，Negative electrode filter plate 5 and anode filter plate 6 are connected with power supply 3 by time switch 4，Aeration tube 13 is arranged on bottom reactor 2，Aeration tube 13 is connected with air pump 9 by effusion meter 7，Valve 8 it is provided with between effusion meter 7 and air pump 9，Water inlet 1 and outlet 10 it is provided with on reactor 2，It is respectively mounted 6 ultrasonic transducers outside two reactor walls parallel with electrofiltration plate，And be symmetrically distributed，Electrofiltration plate is vertical with ultrasonic propagation direction，Ultrasonic transducer is connected with supersonic generator，Electrofiltration interplate spacing is that 40mm(is shown in Fig. 4)；
Reactor is stainless steel reactor, and the opposite at reactor welds ultrasonic transducer, forms parallel plate type ultrasonic reactor, and is connected with supersonic generator, it is ensured that operating power and frequency adapt.Supersonic generator operating frequency and power are respectively 17 kHz and 300 W.The hexagonal distribution of ultrasonic transducer, spacing distance 200 mm between two ultrasonic transducers, the ultrasonic transducer on corresponding surface becomes corresponding distribution, and the spacing installed between two outer walls of ultrasonic transducer is 160 mm；Inside reactor is provided with draw-in groove, makes electrofiltration plate distribution mode vertical with ultrasonic propagation direction.
After 4 pieces of negative electrode filter plates and 4 pieces of anode filter plates are connected respectively, 2 groups of series electrical filter plates are distributed in " male-female-male-female " mode；The electrofiltration plate fixed by gripper shoe is put into reactor draw-in groove fix, then electrofiltration plate is connected with regulated power supply, use pulse voltage, control voltage swing is 0.1V, electrofiltration plate spacing is 40 mm, after switching on power, electrofiltration plate will occur the series reaction such as electro-catalysis, light electrolysis, electricity flocculation.
Coking chemical waste water is in water inlet 1 puts into reactor 2, and the water surface slightly higher than ultrasonic transducer height also covers electrofiltration plate.Opening the aerator of reactor bottom, controlling aeration rate is 70 L h-1.Opening supersonic generator and regulated power supply switch, coking chemical waste water, after supersound process 20 min worked in coordination with by electrofiltration plate, enters next flow process by outlet 10 and carries out biochemical treatment further；COD in the former water of coking chemical waste waterCrConcentration is 3200 mg/L, after treatment, and COD in water outletCrConcentration is less than 1000 mg/L.
Embodiment 2: this electrofiltration plate is negative electrode filter plate and anode filter plate, negative electrode electrofiltration plate includes cathode electrocatalyst material, micro-electrolysis material and conductor material, anode electrofiltration plate includes anode electrocatalysis material, micro-electrolysis material and conductor material, wherein cathode electrocatalyst material is rustless steel, anode electrocatalysis material is titanium manganese alloy, electrocatalysis material is to be the granule (particle length is 5 ~ 15mm, and width is 3 ~ 6mm) that porous plate crushes；Electrofiltration plate thickness is 25 mm, and electrocatalysis material disperses to be mixed in micro-electrolysis material with the ratio of mass ratio 1:1, is then pressed into tabular；Micro-electrolysis material is mixed according to volume ratio 1:1 ratio by ferrum-carbon, it is shaped as porous cylindrical, particle diameter is 60 mesh, micro-electrolysis material increases platinum bits (particle diameter is 60 mesh) that volume ratio is 0.2% and increases the potential difference of filler, add adjuvant polyethylene hollow plastic ball, a diameter of 21 mm of hollow plastic ball；Conductor material selection copper cash, a diameter of 2.5 mm, S-shaped it is distributed in micro-electrolysis stuffing (Fig. 1 b, Fig. 2 b).
nullIt is applied to negative electrode filter plate in the present embodiment and anode filter plate process in high concentrated organic wastewater device，This device includes reactor 2、Power supply 3、Time switch 4、Negative electrode filter plate 5、Anode filter plate 6、Air pump 9、Ultrasonic transducer 11，Supersonic generator 12、Aeration tube 13，Negative electrode filter plate 5 and anode filter plate 6 are arranged in reactor 2 by draw-in groove，Negative electrode filter plate 5 and anode filter plate 6 are connected with power supply 3 by time switch 4，Aeration tube 13 is arranged on bottom reactor 2，Aeration tube 13 is connected with air pump 9 by effusion meter 7，Valve 8 it is provided with between effusion meter 7 and air pump 9，Water inlet 1 and outlet 10 it is provided with on reactor 2，It is respectively mounted 10 ultrasonic transducers outside two reactor walls parallel with electrofiltration plate，It is symmetrically distributed，Electrofiltration plate is vertical with ultrasonic propagation direction，Ultrasonic transducer is connected with supersonic generator，Electrofiltration interplate spacing is 60 mm；
Reactor is stainless steel reactor, and the opposite at reactor welds ultrasonic transducer, forms parallel plate type ultrasonic reactor, and is connected with supersonic generator, it is ensured that operating power and frequency adapt.Supersonic generator operating frequency and power are respectively 42 kHz and 1500 W.The rounded distribution of ultrasonic transducer, spacing distance 300 mm between two ultrasonic transducers, the ultrasonic transducer on corresponding surface becomes corresponding distribution, and the spacing installed between two outer walls of ultrasonic transducer is 180 mm；Inside reactor is provided with draw-in groove, makes electrofiltration plate distribution mode vertical with ultrasonic propagation direction.
After 2 pieces of negative electrode filter plates and 2 pieces of anode filter plates are connected respectively, electrofiltration plate after 2 groups of series connection is with " male-female " such formal distribution, the electrofiltration plate fixed by gripper shoe is put into reactor draw-in groove fix, then electrofiltration plate is connected with regulated power supply, using DC voltage, controlling voltage swing is 4.0 V, and electrofiltration plate spacing is 60 mm, after switching on power, electrofiltration plate will occur the series reaction such as electro-catalysis, light electrolysis, electricity flocculation.
Pharmacy waste water is in water inlet 1 puts into reactor 2, and the water surface slightly higher than ultrasonic transducer height also covers electrofiltration plate.Opening the aerator of reactor bottom, controlling aeration rate is 130 L h-1.Opening supersonic generator and regulated power supply switch, pharmacy waste water, after supersound process 70 min worked in coordination with by electrofiltration plate, enters next flow process by outlet 10 and carries out biochemical treatment further；COD in the former water of pharmacy waste waterCrConcentration is 4000 mg/L, after treatment, and COD in water outletCrConcentration is less than 800 mg/L.
Embodiment 3: this electrofiltration plate is negative electrode filter plate and anode filter plate, negative electrode electrofiltration plate includes cathode electrocatalyst material, micro-electrolysis material and conductor material, anode electrofiltration plate includes anode electrocatalysis material, micro-electrolysis material and conductor material, wherein cathode electrocatalyst material is graphite, anode electrocatalysis material is titanium magnesium alloy, and electrocatalysis material is for being perforated plate-like (aperture 100 mesh)；Electrofiltration plate thickness is 30 mm, and electrocatalysis material is pressed into tabular and is distributed in micro-electrolysis material both sides.Micro-electrolysis material is mixed according to volume ratio 1.2:1 ratio by aluminum-carbon, it is shaped as unsetting granule, particle diameter is 100 mesh, micro-electrolysis material increases the copper scale (particle diameter is 100 mesh) that volume ratio is 0.3% and increases the potential difference of filler, add adjuvant polyethylene hollow plastic ball, a diameter of 20 mm of hollow ball；Conductor material selection nickel wire, specification is 6.0 mm, and 3 nickel wires are that river font is distributed in micro-electrolysis stuffing.
nullIt is applied to negative electrode filter plate in the present embodiment and anode filter plate process in high concentrated organic wastewater device，This device includes reactor 2、Power supply 3、Time switch 4、Negative electrode filter plate 5、Anode filter plate 6、Air pump 9、Ultrasonic transducer 11，Supersonic generator 12、Aeration tube 13，Negative electrode filter plate 5 and anode filter plate 6 are arranged in reactor 2 by draw-in groove，Negative electrode filter plate 5 and anode filter plate 6 are connected with power supply 3 by time switch 4，Aeration tube 13 is arranged on bottom reactor 2，Aeration tube 13 is connected with air pump 9 by effusion meter 7，Valve 8 it is provided with between effusion meter 7 and air pump 9，Water inlet 1 and outlet 10 it is provided with on reactor 2，It is respectively mounted 18 ultrasonic transducers outside two reactor walls parallel with electrofiltration plate，It is symmetrically distributed，Electrofiltration plate is vertical with ultrasonic propagation direction，Ultrasonic transducer is connected with supersonic generator；
Reactor is stainless steel reactor, and the opposite at reactor welds ultrasonic transducer, forms parallel plate type ultrasonic reactor, and is connected with supersonic generator, it is ensured that operating power and frequency adapt.Supersonic generator operating frequency and power are respectively 68 kHz and 2700 W.Ultrasonic transducer distribution triangular in shape, spacing distance 400 mm between two ultrasonic transducers, the ultrasonic transducer on corresponding surface becomes corresponding distribution, and the spacing installed between two outer walls of ultrasonic transducer is 200 mm；Inside reactor is provided with draw-in groove, makes electrofiltration plate distribution mode vertical with ultrasonic propagation direction.
The formal distribution that 2 monolithic negative electrode filter plates and 1 monolithic anode filter plate so replace with " male-female-the moon ", the electrofiltration plate fixed by gripper shoe is put into reactor draw-in groove fix, then electrofiltration plate is connected with regulated power supply, use pulse voltage, control voltage swing is 8.0V, electrofiltration plate spacing is 40 mm, and after switching on power, electrofiltration plate will occur the series reaction such as electro-catalysis, light electrolysis, electricity flocculation.
Petroleum wastewater is in water inlet 1 puts into reactor 2, and the water surface slightly higher than ultrasonic transducer height also covers electrofiltration plate.Opening the aerator of reactor bottom, controlling aeration rate is 200 L h-1.Opening supersonic generator and regulated power supply switch, petroleum wastewater, after supersound process 120 min worked in coordination with by electrofiltration plate, enters next flow process by outlet 10 and carries out biochemical treatment further；COD in the former water of petroleum wastewaterCrConcentration is 18000 mg/L, after treatment, and COD in water outletCrConcentration is less than 1600 mg/L.
Embodiment 4: this electrofiltration plate is anode and cathode integration filter plate, it includes electro-catalysis cathode material, electro-catalysis anode material and micro-electrolysis material, and wherein cathode electrocatalyst material is graphite, and anode electrocatalysis material is titanium magnesium alloy, and structure is perforated plate-like；Electrofiltration plate thickness is 40 mm, and electro-catalysis cathode material and electro-catalysis anode material are distributed in micro-electrolysis material both sides after being pressed into tabular.Micro-electrolysis material is mixed according to volume ratio 1.2:1 ratio by aluminum-carbon, it is shaped as unsetting granule, particle size range is 100 mesh, micro-electrolysis material increases the copper scale (particle diameter is 60 mesh) that volume ratio is 0.3% and increases the potential difference of filler, add adjuvant polyethylene hollow plastic ball, a diameter of 38 mm(Fig. 3 a of hollow ball).
nullIt is applied to anode and cathode integration filter plate in the present embodiment process in high concentrated organic wastewater device，This device includes reactor 2、Power supply 3、Time switch 4、Anode and cathode integration filter plate 18、Air pump 9、Aeration tube 13、Ultrasonic transducer 11，Supersonic generator 12，Anode and cathode integration filter plate 18 is arranged in reactor 2 by draw-in groove，Anode and cathode integration filter plate 18 is connected with power supply 3 by time switch 4，Aeration tube 13 is arranged on bottom reactor 2，Aeration tube 13 is connected with air pump 9 by effusion meter 7，Valve 8 it is provided with between effusion meter 7 and air pump 9，Water inlet 1 and outlet 10 it is provided with on reactor 2，18 ultrasonic transducers are respectively symmetrically and are arranged on outside two parallel with electrofiltration plate reactor wall，Electrofiltration plate is vertical with ultrasonic propagation direction，Ultrasonic transducer is connected with supersonic generator (see figure 5)；
Reactor is stainless steel reactor, and the opposite at reactor welds ultrasonic transducer, forms parallel plate type ultrasonic reactor, and is connected with supersonic generator, it is ensured that operating power and frequency adapt.Supersonic generator operating frequency and power are respectively 68 kHz and 2700 W.Ultrasonic transducer distribution triangular in shape, is spaced 400 mm between two ultrasonic transducers, and the ultrasonic transducer on corresponding surface becomes corresponding distribution, and the spacing installed between two outer walls of ultrasonic transducer is 200 mm；Inside reactor is provided with draw-in groove, makes electrofiltration plate distribution mode vertical with ultrasonic propagation direction.
The electrofiltration plate fixed by gripper shoe is put into reactor draw-in groove fix, then electrofiltration plate is connected with regulated power supply, use pulse voltage, control voltage swing is 8.0V, electrofiltration plate spacing is 80 mm, by polylith anode and cathode integration filter plate series arrangement, after switching on power, electrofiltration plate will occur the series reaction such as electro-catalysis, light electrolysis, electricity flocculation.
Wastewater from chemical industry is in water inlet 1 puts into reactor 2, and the water surface slightly higher than ultrasonic transducer height also covers electrofiltration plate.Opening the aerator of reactor bottom, controlling aeration rate is 200 L h-1.Opening supersonic generator and regulated power supply switch, wastewater from chemical industry, after supersound process 120 min worked in coordination with by electrofiltration plate, enters next flow process by outlet 10 and carries out biochemical treatment further；COD in the former water of wastewater from chemical industryCrConcentration is 16000 mg/L, after treatment, and COD in water outletCrConcentration is less than 1200 mg/L.
Embodiment 5: this electrofiltration plate is anode filter plate and anode and cathode integration filter plate, anode electrofiltration plate includes anode electrocatalysis material, micro-electrolysis material and conductor material, its Anodic electrocatalysis material is the granule (particle length is 5 ~ 15 mm, and width is 3 ~ 6 mm) that Ti-Ni alloy plate crushes；Electrofiltration plate thickness is 10 mm, anode electrocatalysis material disperses to be mixed in micro-electrolysis material with the ratio of mass ratio 1:2, and micro-electrolysis material is mixed according to volume ratio 0.9:1 ratio by ferrum-carbon, conductor material selection copper cash, a diameter of 3.0 mm, Z-shape are distributed in micro-electrolysis stuffing；
Anode and cathode integration filter plate includes electro-catalysis cathode material, electro-catalysis anode material and micro-electrolysis material, wherein cathode electrocatalyst material is the granule that titanium plate crushes, anode electrocatalysis material is the granule that titanium magnesium alloy plate crushes, micro-electrolysis material is mixed according to volume ratio 1.1:1 ratio by aluminum-carbon, it is spherical that it is shaped as granule, particle size range is 40 mesh, electro-catalysis cathode material and electro-catalysis anode material (mass ratio 1:1) are mixed in micro-electrolysis stuffing, and its mixing quality with micro-electrolysis material is than for 1:3(Fig. 3 b).
It is applied to the present embodiment Anodic filter plate and anode and cathode integration filter plate process in high concentrated organic wastewater device, apparatus structure is with embodiment 1, and difference is that the 2 pieces of anode filter plate connected filter plates integrated with anode and cathode are alternately distributed in reactor with " sun-integration-integration-sun "；Use the present embodiment device Treatment of Wastewater in Coking, COD in the former water of coking chemical waste waterCrConcentration is 3200 mg/L, after treatment, and COD in water outletCrConcentration is less than 800 mg/L.
Embodiment 6: this electrofiltration plate is negative electrode filter plate and anode and cathode integration filter plate, negative electrode electrofiltration plate includes cathode electrocatalyst material, micro-electrolysis material and conductor material, wherein cathode electrocatalyst material is titanium plate, cathode electrocatalyst material is arranged at micro-electrolysis stuffing both sides, structure is perforated plate-like, on porous plate, aperture is 200 mesh, and electrofiltration plate thickness is 10 mm.Micro-electrolysis material is mixed according to volume ratio 1:1 ratio by ferrum-carbon, conductor material selection nickel wire, a diameter of 5.0 mm, Z-shape is distributed in micro-electrolysis stuffing；
Anode and cathode integration filter plate includes electro-catalysis cathode material, electro-catalysis anode material and micro-electrolysis material, wherein cathode electrocatalyst material is the granule that graphite crushes, anode electrocatalysis material is the granule that Ti-Ni alloy plate crushes, micro-electrolysis material is mixed according to volume ratio 1:1 ratio by aluminum-carbon, it is spherical that it is shaped as granule, particle size range is 70 mesh, electro-catalysis cathode material and electro-catalysis anode material (mass ratio 2:1) are mixed in micro-electrolysis stuffing, and its mixing quality with micro-electrolysis material is than for 1:1.
It is applied to negative electrode filter plate in the present embodiment and anode and cathode integration filter plate process in high concentrated organic wastewater device, apparatus structure is with embodiment 1, and difference is that the 3 pieces of negative electrode filter plate connected filter plates integrated with anode and cathode are alternately distributed in reactor with " integration-cloudy-integration "；The present embodiment device is used to process petroleum wastewater, COD in the former water of petroleum wastewaterCrConcentration is 18000 mg/L, after treatment, and COD in water outletCrConcentration is less than 2000 mg/L.
Embodiment 7: this electrofiltration plate is negative electrode filter plate, anode filter plate, anode and cathode integration filter plate, negative electrode electrofiltration plate includes cathode electrocatalyst material, micro-electrolysis material and conductor material, anode electrofiltration plate includes anode electrocatalysis material, micro-electrolysis material and conductor material, wherein cathode electrocatalyst material is rustless steel, anode electrocatalysis material is Ti-Ni alloy plate, structure is perforated plate-like, and on porous plate, the aperture in hole is 100 mesh；Electrofiltration plate thickness is 20 mm, and electrocatalysis material is pressed into tabular and is distributed in micro-electrolysis material both sides；Micro-electrolysis material is mixed according to volume ratio 0.8:1 ratio by aluminum-carbon, and it is spherical that it is shaped as granule, and particle size range is 18 mesh, conductor material selection nickel wire, and specification is 0.8 mm, S-shaped is distributed in micro-electrolysis stuffing.
Anode and cathode integration filter plate includes electro-catalysis cathode material, electro-catalysis anode material and micro-electrolysis material, wherein cathode electrocatalyst material is graphite, anode electrocatalysis material is Ti-Ni alloy plate, electro-catalysis cathode material and electro-catalysis anode material are distributed in micro-electrolysis material both sides after being pressed into tabular, micro-electrolysis material is mixed according to volume ratio 1:1 ratio by aluminum-carbon, it is spherical that it is shaped as granule, particle size range is 70 mesh, increases the copper scale (particle diameter is 40 mesh) that volume ratio is 0.15% and increase the potential difference of filler in micro-electrolysis material.
It is applied to process in high concentrated organic wastewater device by negative electrode filter plate, anode filter plate, anode and cathode integration filter plate in the present embodiment, apparatus structure is with embodiment 1, and difference is that 2 pieces of negative electrode filter plates connected, 2 pieces of series connection anode filter plates, anode and cathode integration filter plates are alternately distributed in reactor；The present embodiment device is used to process dyeing waste water, COD in the former water of dyeing waste waterCrConcentration is 13000 mg/L, after treatment, and COD in water outletCrConcentration is less than 2400 mg/L.
Claims (10)
1. an electrofiltration plate, it is characterised in that: it is made anode and cathode integration filter plate, anode electrocatalysis material and cathode electrocatalyst material be mixed in micro-electrolysis stuffing by anode electrocatalysis material, cathode electrocatalyst material, micro-electrolysis material；Or made plate-shaped anode filter plate or negative electrode filter plate, anode electrocatalysis material or cathode electrocatalyst material and be arranged at micro-electrolysis stuffing both sides by anode electrocatalysis material or cathode electrocatalyst material, micro-electrolysis material, conductive material or be mixed in micro-electrolysis stuffing；When electrocatalysis material is mixed in micro-electrolysis material, being pressed into tabular, the mixing quality of electrocatalysis material and micro-electrolysis material is than for 1:1 ~ 1:3；During preparation anode and cathode integration electrofiltration plate, the mixing quality of anode electrocatalysis material and cathode electrocatalyst material ratio is for 2:1 ~ 1:1.
Electrofiltration plate the most according to claim 1, it is characterized in that: cathode electrocatalyst material is titanium, rustless steel or graphite, anode electrocatalysis material is Ti-Ni alloy, the violent alloy of titanium or titanium magnesium alloy, electrocatalysis material is perforated plate-like or the granule formed by porous plate shearing-crushing, on porous plate, the aperture in hole is 30 ~ 200 mesh, the broken particle length formed is 5 ~ 15mm, and width is 3 ~ 6mm.
Electrofiltration plate the most according to claim 1, it is characterised in that: micro-electrolysis material is mixed by ferrum-carbon or aluminum-carbon, and its mixed volume is than for 0.8:1 ~ 1.2:1.
4. according to electrofiltration plate described in claim 3, it is characterised in that: micro-electrolysis material also includes that copper scale or the platinum bits that percent by volume is 0.1% ~ 0.3%, copper scale or platinum bits particle diameter are 18 ~ 100 mesh.
5. according to electrofiltration plate described in claim 3 or 4, it is characterised in that: possibly together with polyethylene hollow plastic ball or polypropylene hollow baton round in micro-electrolysis stuffing, a diameter of 5 ~ 38 mm of hollow plastic ball.
6. according to electrofiltration plate described in claim 1, it is characterised in that: conductive material is a diameter of 0.8 ~ 6.0 mm of copper cash or nickel wire, copper cash or nickel wire, S-shaped, Z-shaped is distributed in micro-electrolysis material, is distributed if conductive material is more than one in river font.
7. according to electrofiltration plate described in claim 5, it is characterised in that: electrofiltration plate thickness is 10 ~ 50 mm.
null8. use the process high concentrated organic wastewater device of electrofiltration plate described in claim 1，It is characterized in that: include reactor (2)、Power supply (3)、Time switch (4)、The electrofiltration plate of more than two pieces、Air pump (9)、Ultrasonic transducer (11)、Supersonic generator (12)、Aeration tube (13)，Electrofiltration plate is arranged in reactor (2) by draw-in groove，Electrofiltration plate is connected with power supply (3) by time switch (4)，Aeration tube (13) is arranged on reactor (2) bottom，Aeration tube (13) is connected with air pump (9) by effusion meter (7)，Reactor is provided with water inlet and outlet on (2)，Two or more ultrasonic transducer (11) is symmetrically mounted on outside two parallel with electrofiltration plate reactor wall，Electrofiltration plate is vertical with ultrasonic propagation direction，Ultrasonic transducer is connected with supersonic generator，Electrofiltration interplate spacing is 40 ~ 80 mm；
Wherein the set-up mode of electrofiltration plate is as follows:
A, monolithic anode filter plate and monolithic negative electrode filter plate use the over-over mode of " sun-male-female-the moon " to be distributed in reactor；
B, by 2 ~ 4 pieces series connection anode filter plates and 2 ~ 4 pieces of series cathode filter plates be distributed in reactor with the over-over mode of " sun-male-female-the moon ", again series connection anode filter plate and series cathode filter plate are coupled together after setting；
C, when in reactor electrofiltration plate be 1 ~ 4 piece of series connection anode filter plate or 1 ~ 4 piece of series cathode filter plate with the combination of more than 1 piece anode and cathode integration filter plate time, connect anode filter plate or series cathode filter plate filter plate integrated with anode and cathode be alternately distributed in reactor；
D, when in reactor, electrofiltration plate is 1 ~ 4 piece of series connection anode filter plate, 1 ~ 4 piece of series cathode filter plate and the combination of more than 1 piece anode and cathode integration filter plate, the electrofiltration plate of three types is alternately distributed in reactor；
E, when in reactor electrofiltration plate be the anode and cathode integration filter plate of more than 1 piece, itself and power sources in series.
Process high concentrated organic wastewater device the most according to claim 8, it is characterized in that: the ultrasonic transducer on reactor outer wall is hexagonal, circular or Triangle-Profile, spacing distance between two ultrasonic transducers is 200 ~ 400 mm, and the spacing installed between two outer walls of ultrasonic transducer is 160 ~ 200 mm.
Process high concentrated organic wastewater device the most according to claim 9, it is characterised in that: supersonic generator uses power to be 300 ~ 2700 W, and using frequency is 17 ~ 68 kHz, and electrofiltration plate applied voltage is 0.1 ~ 8.0 V, and aeration rate scope is 70 ~ 200 L h-1。
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| CN105749895A (en) * | 2016-04-12 | 2016-07-13 | 中冶华天工程技术有限公司 | Preparation method of alumina-carbon catalyst for treating organic wastewater |
| CN106882900A (en) * | 2017-02-27 | 2017-06-23 | 南京元凯生物能源环保工程有限公司 | A kind of later stage depth processing unit of organic wastewater and its technological process |
| CN111847595B (en) * | 2019-04-30 | 2022-10-21 | 中关村至臻环保股份有限公司 | Nano electrochemical reaction device |
| CN112723492B (en) * | 2020-12-18 | 2023-05-26 | 广州市铁鑫金属结构有限公司 | Preparation method and application of cuprous oxide-loaded activated carbon |
| CN112678922B (en) * | 2020-12-18 | 2023-07-18 | 宁夏新力新能源科技有限公司 | Electrochemical water treatment device and system |
| CN112607969B (en) * | 2020-12-18 | 2023-10-31 | 湖北紫诺新材料科技股份有限公司 | Dye wastewater treatment process |
| CN113292143B (en) * | 2021-05-10 | 2023-03-24 | 昆明理工大学 | Method for selectively separating anions and cations in salt-containing wastewater by electric field coupling composite electric filter membrane |
| CN114890498B (en) * | 2021-07-01 | 2023-09-19 | 南京诺兰环境工程技术有限公司 | Operation method of circulating photocatalytic device |
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