CN104003481A - Electrical filter board and application of same in highly concentrated organic wastewater - Google Patents
Electrical filter board and application of same in highly concentrated organic wastewater Download PDFInfo
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- 239000002351 wastewater Substances 0.000 title claims abstract description 49
- 239000000463 material Substances 0.000 claims abstract description 161
- 239000004020 conductor Substances 0.000 claims abstract description 27
- 238000011043 electrofiltration Methods 0.000 claims description 118
- 238000005868 electrolysis reaction Methods 0.000 claims description 86
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 39
- 230000005611 electricity Effects 0.000 claims description 38
- 239000002245 particle Substances 0.000 claims description 36
- 230000003197 catalytic effect Effects 0.000 claims description 27
- 238000005273 aeration Methods 0.000 claims description 26
- 238000009826 distribution Methods 0.000 claims description 17
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 14
- 229910052802 copper Inorganic materials 0.000 claims description 14
- 239000010949 copper Substances 0.000 claims description 14
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 10
- RQMIWLMVTCKXAQ-UHFFFAOYSA-N [AlH3].[C] Chemical compound [AlH3].[C] RQMIWLMVTCKXAQ-UHFFFAOYSA-N 0.000 claims description 9
- 239000010935 stainless steel Substances 0.000 claims description 9
- 229910001220 stainless steel Inorganic materials 0.000 claims description 9
- 229920000426 Microplastic Polymers 0.000 claims description 8
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 8
- -1 polyethylene Polymers 0.000 claims description 8
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 7
- 229910004337 Ti-Ni Inorganic materials 0.000 claims description 7
- 229910011209 Ti—Ni Inorganic materials 0.000 claims description 7
- 229910045601 alloy Inorganic materials 0.000 claims description 7
- 239000000956 alloy Substances 0.000 claims description 7
- KHYBPSFKEHXSLX-UHFFFAOYSA-N iminotitanium Chemical compound [Ti]=N KHYBPSFKEHXSLX-UHFFFAOYSA-N 0.000 claims description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
- 239000004698 Polyethylene Substances 0.000 claims description 6
- 239000010439 graphite Substances 0.000 claims description 6
- 229910002804 graphite Inorganic materials 0.000 claims description 6
- 238000009434 installation Methods 0.000 claims description 6
- QMQXDJATSGGYDR-UHFFFAOYSA-N methylidyneiron Chemical compound [C].[Fe] QMQXDJATSGGYDR-UHFFFAOYSA-N 0.000 claims description 6
- 229920000573 polyethylene Polymers 0.000 claims description 6
- 229910000861 Mg alloy Inorganic materials 0.000 claims description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 5
- SXSVTGQIXJXKJR-UHFFFAOYSA-N [Mg].[Ti] Chemical compound [Mg].[Ti] SXSVTGQIXJXKJR-UHFFFAOYSA-N 0.000 claims description 5
- 239000010936 titanium Substances 0.000 claims description 5
- 229910052719 titanium Inorganic materials 0.000 claims description 5
- 229910052697 platinum Inorganic materials 0.000 claims description 4
- 239000004743 Polypropylene Substances 0.000 claims description 2
- 229910001069 Ti alloy Inorganic materials 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 229920001155 polypropylene Polymers 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 10
- 230000000694 effects Effects 0.000 abstract description 10
- 238000005189 flocculation Methods 0.000 abstract description 8
- 230000016615 flocculation Effects 0.000 abstract description 8
- 150000001875 compounds Chemical class 0.000 abstract description 6
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- 150000002894 organic compounds Chemical class 0.000 abstract description 3
- 238000002161 passivation Methods 0.000 abstract description 3
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- 238000009210 therapy by ultrasound Methods 0.000 abstract 2
- 230000009257 reactivity Effects 0.000 abstract 1
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- 238000003466 welding Methods 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
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- 238000010586 diagram Methods 0.000 description 4
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- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 239000008186 active pharmaceutical agent Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
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- NJFMNPFATSYWHB-UHFFFAOYSA-N ac1l9hgr Chemical compound [Fe].[Fe] NJFMNPFATSYWHB-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- JUPQTSLXMOCDHR-UHFFFAOYSA-N benzene-1,4-diol;bis(4-fluorophenyl)methanone Chemical compound OC1=CC=C(O)C=C1.C1=CC(F)=CC=C1C(=O)C1=CC=C(F)C=C1 JUPQTSLXMOCDHR-UHFFFAOYSA-N 0.000 description 1
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- MECMQNITHCOSAF-UHFFFAOYSA-N manganese titanium Chemical compound [Ti].[Mn] MECMQNITHCOSAF-UHFFFAOYSA-N 0.000 description 1
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- 229910052759 nickel Inorganic materials 0.000 description 1
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- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention relates to an electrical filter board which is an anode-cathode integrated filter board prepared from an anode electrocatalysis material, a cathode electrocatalysis material and a microelectrolysis material or a plate-shaped anode or cathode filter board prepared from the anode or cathode electrocatalysis material, the microelectrolysis material and a conductive material. When the electrical filter board is cooperatively used with a novel parallel plate-type ultrasonic reactor in treatment of highly concentrated organic wastewater, a substantial synergistic effect is obtained; organic compounds in the wastewater are degraded into micromolecular compounds through reactions like electrocatalysis, microelectrolysis and electric flocculation initiated by the electrical filter board and through strongly oxidizing .OH generated by ultrasonic treatment, so biodegradability of the wastewater is improved; moreover, a mechanical shearing effect generated by ultrasonic treatment can effectively clean oxides on the electrical filter board, so disadvantages that a traditional electrocatalysis material easily undergoes inactivation and passivation and a traditional microelectrolysis material easily undergoes hardening are overcome, electrochemical reactivity is guaranteed, and treating efficiency is improved.
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 Chemicals are applied to all trades and professions, in the heavily contaminated industry such as particularly coking, chemical industry, plating, printing and dyeing, improving the quality of products, in quality, also brought day by day serious problem of environmental pollution, be mainly manifested in: Organic Pollutants in Wastewater concentration is high, Stability Analysis of Structures, biochemical are poor, common process is difficult to realize qualified discharge, and processing cost is high, realizes the target of energy-saving and emission-reduction bring enormous pressure to enterprise.Organic waste water particularly high salt high concentrated organic wastewater is processed, and is the difficult problem that numerous domestic efforts at environmental protection Zhe Ji administrative authority pays close attention to always.
The micro-electrolyzer major part of tradition is fixed bed, and filler generally adopts iron carbon mixture, is characterized in simple in structure, good fluidity, but still there are some practicality problems: mixed fillers is overlapped to be overstock, and easily causes a body to harden, form short circuit and dead band, processing efficiency is reduced; Iron iron amount of stripping under acidic conditions is large, supplements iron filings labour intensity large.Supersound process can be converted into micromolecular compound by larger molecular organics in waste water by its cavitation effect, mechanical shearing and micro-throwing out, thereby improves wastewater biodegradability.But applications of ultrasound, when high concentrated organic wastewater is processed, often cannot obtain gratifying effect, and energy consumption is higher, thereby has been limited the industrial applications of this treatment technology separately.
Summary of the invention
The object of the invention is filler when solving existing micro-electrolyzer practical application easily hardens, inactivation, work-ing life is short, change the large shortcoming of filler labour intensity, a kind of electrofiltration plate is provided, it is by anode electrocatalysis material, cathodic electricity catalytic material, micro-electrolysis material is made the integrated filter plate of tabular anode and cathode, or by anode electrocatalysis material or cathodic electricity catalytic material, micro-electrolysis material, electro-conductive material is made plate-shaped anode filter plate or negative electrode filter plate, anode electrocatalysis material and/or cathodic electricity catalytic 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, be pressed into tabularly, the mixing quality of electrocatalysis material and micro-electrolysis material is than being 1:1 ~ 1:3, during the integrated electrofiltration plate of preparation anode and cathode, anode electrocatalysis material is 2:1 ~ 1:1 with the mixing quality ratio of cathodic electricity catalytic material.
Described cathodic electricity catalytic material is titanium, stainless steel or graphite, anode electrocatalysis material is Ti-Ni alloy, the violent alloy of titanium or titanium magnesium alloy, electrocatalysis material is porous particle tabular or that formed by porous plate shearing-crushing, on porous plate, the aperture in hole is 30 ~ 200 orders, the broken particle length forming is 5 ~ 15mm, and width is 3 ~ 6mm.
Described micro-electrolysis material is mixed by iron-carbon or aluminium-carbon, and its mixed volume is than being 0.8:1 ~ 1.2:1; The variation of micro-electrolysis mixed fillers shape, has that particle is spherical, porous cylindrical or a unsetting particle; Micro-electrolysis stuffing grain diameter scope is 18 ~ 100 orders, and during use, the cycle of interpolation or replacing filler is 1 ~ March; In micro-electrolysis material, can suitably add volume percent and be 0.1% ~ 0.3% copper scale or platinum bits (particle diameter is 18 ~ 100 orders), potential difference for increasing filler, thereby can also add auxiliary material effectively avoids filler to occur the phenomenon that hardens, also be conducive to solid-liquid fully contacts simultaneously, promote treatment effect, auxiliary material is selected polyethylene or polypropylene hollow baton round, and hollow plastic pellet diameter is 5 ~ 38mm.
Described electro-conductive material is copper cash or nickel wire, and copper cash or nickel wire diameter are 0.8 ~ 6.0 mm, and S-shaped, Z-shaped being distributed in micro-electrolysis material is river font distribution above if electro-conductive material is one; , conductor material length is determined according to electrofiltration plate size, guarantees that the energising of electrofiltration plate is without dead angle.
Electrofiltration plate thickness of the present invention is 10 ~ 50 mm, on electrofiltration plate, can be provided with bracing frame, and bracing frame is made by tetrafluoroethylene or polyethers ether resin of copper (PEEK resin) material, is wrapped in electrofiltration plate surrounding.
Another object of the present invention is for the treatment of in high concentrated organic wastewater device by electrofiltration plate, this device comprises reactor 2, power supply 3, time switch 4, two blocks of above electrofiltration plates, pneumatic pump 9, ultrasonic transducer 11, ultrasonic 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 bottoms, aeration tube 13 is connected with pneumatic pump 9 by under meter 7, on reactor 2, be provided with water-in and water outlet, two above ultrasonic transducer 11 symmetries are arranged on two the reactor wall outsides parallel with electrofiltration plate, electrofiltration plate is vertical with ultrasonic propagation direction, ultrasonic transducer is connected with ultrasonic generator, between electrofiltration plate, spacing is the distance between the dissimilar electrofiltration plate of 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 adopt 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 during more than negative electrode filter plate, the oxidizing reaction occurring in reactor is occupied an leading position, and at this moment take and processes waste water that reductive organic matter concentration is high as main; When negative electrode filter plate quantity is during more than anode filter plate, the reduction reaction occurring in reactor is occupied an leading position, and at this moment take and processes waste water that oxidisability organic concentration is high as main;
B, the over-over mode by 2 ~ 4 series connection anode filter plates and 2 ~ 4 series connection negative electrode filter plates with " sun-male-female-the moon (sun-male-female, male-female-yin, yang-the moon) " are distributed in reactor, after setting, series connection anode filter plate and the negative electrode filter plate of connecting are coupled together again;
C, in reactor, electrofiltration plate is 1 ~ 4 series connection anode filter plate or 1 ~ 4 series connection negative electrode filter plate during with the integrated filter plate combination of more than 1 anode and cathode, and series connection anode filter plate or series connection negative electrode filter plate and the integrated filter plate of anode and cathode are distributed in reactor with " sun/the moon-integrated-integrated-Yang/the moon-integrated (integrated-Yang/the moon-integrated, positive/the moon-integrated) " over-over mode;
D, in reactor, electrofiltration plate is 1 ~ 4 series connection anode filter plate, 1 ~ 4 series connection negative electrode filter plate and when more than 1 the integrated filter plate of anode and cathode combines, and the electrofiltration plate of three types is alternately distributed in reactor;
E, in reactor, electrofiltration plate is more than 1 integrated filter plate of anode and cathode, and it is connected with power supply.
Ultrasonic transducer at stainless steel reactor opposite face welding equal amts, forms parallel plate type ultrasonic reactor, and is connected with ultrasonic generator, guarantees that operating power and frequency adapt.Ultrasonic generator operating frequency and power range are respectively 17 ~ 68 kHz and 300 ~ 2700 W.
Ultrasonic transducer on described reactor outer wall is regular shape as hexagon, circle or Triangle-Profile, spacing distance between two ultrasonic transducers is 200 ~ 400 mm, ultrasonic transducer on corresponding reactor outer wall is symmetrically distributed, and the spacing between two outer walls of installation 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 fixing by back up pad is put into reactor draw-in groove fixing, then electrofiltration plate is connected with voltage stabilized source, can adopt pulsed voltage, volts DS or voltage of alternating current, voltage range is 0.1 ~ 8.0V, electrofiltration distance between plates is 40 ~ 80 mm, after switching on power, will there is the series reaction such as electrocatalysis, micro-electrolysis, electricity flocculation in electrofiltration plate.Reactor bottom is provided with aeration tube, and aeration rate is 70 ~ 200 Lh
-1.
During use, high concentrated organic wastewater is put into reactor through water-in, the water surface slightly exceeds ultrasonic transducer height and covers electrofiltration plate, open the aerating apparatus of reactor bottom, open ultrasonic generator and power switch, high concentrated organic wastewater, after collaborative supersound process 20 ~ 120 min of electrofiltration plate, enters next flow process by water outlet and further carries out biochemical treatment.
In high concentrated organic wastewater, organism is mainly degraded by following two kinds of modes: 1. electrofiltration plate effect, reduction reaction and micro-electrolysis stuffing that the oxidizing reaction that the anode surface of anode filter plate surface or the integrated filter plate of anode and cathode occurs and the cathode surface of negative electrode filter plate or the integrated filter plate of anode and cathode occur form the redox reaction occurring after galvanic cell, these redox reactions can effectively be degraded into micromolecular compound by macromolecular organic compound, simultaneously anode electrocatalysis material and micro-electrolysis material anode due to occur product that electrocorrosion generates also can with waste water in pollutent further there is redox reaction, produce absorption, flocculation sediment etc., realize the object of further removing pollutent.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 to easily degraded or small organic molecule.And ultrasonic wave has cleanup action, can effectively remove electrode surface oxide compound, prevent that the passivation of electrocatalysis material inactivation, micro-electrolysis stuffing from hardening, thereby guarantee work-ing life and the processing efficiency of electrofiltration plate.In addition, reactor bottom arranges aerating apparatus, when providing a large amount of cavitation nucleus strengthening supersound process efficiency for ultrasonic cavitation effect, also effectively improves the potential difference between micro-electrolysis stuffing, increase galvanic cell reaction, accelerate iron/aluminium bits surface reaction thing and liquid material exchange speed.Water outlet biodegradability after co-treatment significantly improves, effectively reduce follow-up biochemical intractability, and while using due to electrofiltration plate, impressed voltage is low, energy consumption is little, and treatment effect is obviously better than traditional micro-electrolyzer, therefore electrofiltration plate is having using value and prospect very much aspect high concentrated organic wastewater processing.
The present invention is as follows with respect to advantage and the technique effect of prior art:
The strong oxidizing property OH that the reactions such as the electrocatalysis that 1, Coal Gas Washing Cycling Water organic compound causes by electrofiltration plate, micro-electrolysis, electricity flocculation and ultrasonic cavitation effect produce is degraded, and becomes micromolecular compound, and the biodegradability of organic waste water is improved;
2, the mechanical shearing interaction energy that ultrasonic wave produces effectively cleans oxide compound on electrofiltration plate, thereby overcomes the shortcoming that the easy inactivation passivation of traditional electrical catalytic material, micro-electrolysis material are easily hardened, and guarantees that electrochemical reaction is active, effectively improves processing efficiency;
While 3, electrofiltration plate being applied to high concentrated organic wastewater processing, mode of connection is various, the formal distribution totally replacing like this with male-female, and the board-like ultrasonic reactor of coupling novel parallel, acts synergistically significantly simultaneously;
4, impressed voltage is low, and less energy consumption is conducive to realize the object of energy-saving and emission-reduction;
The inventive method is workable, and technological design is simple, with low cost, can efficiently reduce organic content in waste water, improve wastewater biodegradability, for subsequent disposal realizes qualified discharge or recycling is laid good basis, in high concentrated organic wastewater is processed, there is applications well prospect.
Accompanying drawing explanation
Fig. 1 is cathodic electricity filter-plate structure schematic diagram of the present invention, and conductor material distributes and take S shape as example, 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 distributes and take S shape as example, 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 the integrated electrofiltration plate structure of anode and cathode of the present invention schematic diagram, 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 that the present invention uses the processing high concentrated organic wastewater device of the integrated filter plate of anode and cathode;
In figure: 1-water-in; 2-reactor body; 3-power supply; 4-time switch; 5-negative electrode filter plate; 6-anode filter plate; 7-gas meter; 8-valve; 9-pneumatic pump; 10-water outlet; 11-ultrasonic transducer; 12-ultrasonic generator; 13-aeration tube; 14-anode electrocatalysis material; 15-cathodic electricity catalytic material; 16-micro-electrolysis material; 17-electro-conductive material, the integrated filter plate of 18-anode and cathode.
Embodiment
Below in conjunction with drawings and Examples, the present invention is described in further detail, 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, cathodic electricity filter plate comprises cathodic electricity catalytic material, micro-electrolysis material and conductor material, anode electrofiltration plate comprises anode electrocatalysis material, micro-electrolysis material and conductor material, wherein cathodic electricity catalytic material is titanium, anode electrocatalysis material is Ti-Ni alloy plate, it is tabular that structure is porous, and on porous plate, the aperture in hole is 30 orders; Electrofiltration plate thickness is 10 mm, and electrocatalysis material is pressed into the tabular micro-electrolysis material both sides that are distributed in; Micro-electrolysis material is mixed according to volume ratio 0.8:1 ratio by aluminium-carbon, it is spherical that it is shaped as particle, particle size range is 18 orders, in micro-electrolysis material, increasing volume ratio and be 0.1% copper scale (particle diameter is 18 orders) increases the potential difference of filler, add auxiliary material polyethylene hollow plastic pellet, hollow ball diameter is 5 mm; Conductor material is selected nickel wire, and specification is 0.8 mm, and S-shaped being distributed in micro-electrolysis stuffing (seen Fig. 1 a, Fig. 2 a).
Negative electrode filter plate in the present embodiment and anode filter plate are applied to process in high concentrated organic wastewater device, this device comprises reactor 2, power supply 3, time switch 4, negative electrode filter plate 5, anode filter plate 6, pneumatic pump 9, ultrasonic transducer 11, ultrasonic 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 reactor 2 bottoms, aeration tube 13 is connected with pneumatic pump 9 by under meter 7, 9 of under meter 7 and pneumatic pumps are provided with valve 8, on reactor 2, be provided with water-in 1 and water outlet 10, 6 ultrasonic transducers are all installed in two the reactor wall outsides parallel with electrofiltration plate, and be symmetrically distributed, electrofiltration plate is vertical with ultrasonic propagation direction, ultrasonic transducer is connected with ultrasonic generator, between electrofiltration plate, spacing is that 40mm(is shown in Fig. 4),
Reactor is stainless steel reactor, and the opposite face welding ultrasonic transducer at reactor, forms parallel plate type ultrasonic reactor, and be connected with ultrasonic generator, guarantees that operating power and frequency adapt.Ultrasonic generator operating frequency and power are respectively 17 kHz and 300 W.Ultrasonic transducer is hexagon and distributes, spacing distance 200 mm between two ultrasonic transducers, and the ultrasonic transducer on corresponding surface becomes corresponding distribution, and the spacing between two outer walls of installation 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 negative electrode filter plates and 4 anode filter plates are connected respectively, 2 groups of series electrical filter plates distribute in " male-female-male-female " mode; The electrofiltration plate fixing by back up pad is put into reactor draw-in groove fixing, then electrofiltration plate is connected with voltage stabilized source, adopt pulsed voltage, control voltage swing is 0.1V, electrofiltration distance between plates is 40 mm, after switching on power, will there is the series reaction such as electrocatalysis, micro-electrolysis, electricity flocculation in electrofiltration plate.
Coking chemical waste water is put into reactor 2 through water-in 1, and the water surface slightly exceeds ultrasonic transducer height and covers electrofiltration plate.Open the aerating apparatus of reactor bottom, controlling aeration rate is 70 Lh
-1.Open ultrasonic generator and voltage stabilized source switch, coking chemical waste water, after collaborative supersound process 20 min of electrofiltration plate, enters next flow process by water outlet 10 and further carries out biochemical treatment; COD in the former water of coking chemical waste water
crconcentration is 3200 mg/L, after treatment, and COD in water outlet
crconcentration is less than 1000 mg/L.
Embodiment 2: this electrofiltration plate is negative electrode filter plate and anode filter plate, cathodic electricity filter plate comprises cathodic electricity catalytic material, micro-electrolysis material and conductor material, anode electrofiltration plate comprises anode electrocatalysis material, micro-electrolysis material and conductor material, wherein cathodic electricity catalytic material is stainless steel, anode electrocatalysis material is titanium manganese alloy, electrocatalysis material is to be the particle (particle length is 5 ~ 15mm, and width is 3 ~ 6mm) that porous plate fragmentation forms; 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 iron-carbon, it is shaped as porous cylindrical, particle diameter is 60 orders, in micro-electrolysis material, increasing volume ratio and be 0.2% platinum bits (particle diameter is 60 orders) increases the potential difference of filler, add auxiliary material polyethylene hollow plastic pellet, hollow plastic pellet diameter is 21 mm; Conductor material is selected copper cash, and diameter is 2.5 mm, is S-shapedly distributed in (Fig. 1 b, Fig. 2 b) in micro-electrolysis stuffing.
Negative electrode filter plate in the present embodiment and anode filter plate are applied to process in high concentrated organic wastewater device, this device comprises reactor 2, power supply 3, time switch 4, negative electrode filter plate 5, anode filter plate 6, pneumatic pump 9, ultrasonic transducer 11, ultrasonic 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 is connected with power supply 3 by time switch 4 with anode filter plate 6, aeration tube 13 is arranged on reactor 2 bottoms, aeration tube 13 is connected with pneumatic pump 9 by under meter 7, 9 of under meter 7 and pneumatic pumps are provided with valve 8, on reactor 2, be provided with water-in 1 and water outlet 10, 10 ultrasonic transducers are all installed in two the reactor wall outsides parallel with electrofiltration plate, be symmetrically distributed, electrofiltration plate is vertical with ultrasonic propagation direction, ultrasonic transducer is connected with ultrasonic generator, between electrofiltration plate, spacing is 60 mm,
Reactor is stainless steel reactor, and the opposite face welding ultrasonic transducer at reactor, forms parallel plate type ultrasonic reactor, and be connected with ultrasonic generator, guarantees that operating power and frequency adapt.Ultrasonic 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 between two outer walls of installation 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 negative electrode filter plates and 2 anode filter plates are connected respectively, electrofiltration plate after 2 groups of series connection is with " male-female " such formal distribution, the electrofiltration plate fixing by back up pad is put into reactor draw-in groove fixing, then electrofiltration plate is connected with voltage stabilized source, adopt volts DS, controlling voltage swing is 4.0 V, and electrofiltration distance between plates is 60 mm, after switching on power, will there is the series reaction such as electrocatalysis, micro-electrolysis, electricity flocculation in electrofiltration plate.
Pharmacy waste water is put into reactor 2 through water-in 1, and the water surface slightly exceeds ultrasonic transducer height and covers electrofiltration plate.Open the aerating apparatus of reactor bottom, controlling aeration rate is 130 Lh
-1.Open ultrasonic generator and voltage stabilized source switch, pharmacy waste water, after collaborative supersound process 70 min of electrofiltration plate, enters next flow process by water outlet 10 and further carries out biochemical treatment; COD in the former water of pharmacy waste water
crconcentration is 4000 mg/L, after treatment, and COD in water outlet
crconcentration is less than 800 mg/L.
Embodiment 3: this electrofiltration plate is negative electrode filter plate and anode filter plate, cathodic electricity filter plate comprises cathodic electricity catalytic material, micro-electrolysis material and conductor material, anode electrofiltration plate comprises anode electrocatalysis material, micro-electrolysis material and conductor material, wherein cathodic electricity catalytic material is graphite, anode electrocatalysis material is titanium magnesium alloy, and electrocatalysis material is for being porous tabular (aperture 100 orders); Electrofiltration plate thickness is 30 mm, and electrocatalysis material is pressed into the tabular micro-electrolysis material both sides that are distributed in.Micro-electrolysis material is mixed according to volume ratio 1.2:1 ratio by aluminium-carbon, it is shaped as unsetting particle, particle diameter is 100 orders, in micro-electrolysis material, increasing volume ratio and be 0.3% copper scale (particle diameter is 100 orders) increases the potential difference of filler, add auxiliary material polyethylene hollow plastic pellet, hollow ball diameter is 20 mm; Conductor material is selected nickel wire, and specification is 6.0 mm, and 3 nickel wires are river font and are distributed in micro-electrolysis stuffing.
Negative electrode filter plate in the present embodiment and anode filter plate are applied to process in high concentrated organic wastewater device, this device comprises reactor 2, power supply 3, time switch 4, negative electrode filter plate 5, anode filter plate 6, pneumatic pump 9, ultrasonic transducer 11, ultrasonic 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 is connected with power supply 3 by time switch 4 with anode filter plate 6, aeration tube 13 is arranged on reactor 2 bottoms, aeration tube 13 is connected with pneumatic pump 9 by under meter 7, 9 of under meter 7 and pneumatic pumps are provided with valve 8, on reactor 2, be provided with water-in 1 and water outlet 10, 18 ultrasonic transducers are all installed in two the reactor wall outsides parallel with electrofiltration plate, be symmetrically distributed, electrofiltration plate is vertical with ultrasonic propagation direction, ultrasonic transducer is connected with ultrasonic generator,
Reactor is stainless steel reactor, and the opposite face welding ultrasonic transducer at reactor, forms parallel plate type ultrasonic reactor, and be connected with ultrasonic generator, guarantees that operating power and frequency adapt.Ultrasonic 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 between two outer walls of installation ultrasonic transducer is 200 mm; Inside reactor is provided with draw-in groove, makes electrofiltration plate distribution mode vertical with ultrasonic propagation direction.
2 monolithic negative electrode filter plates and 1 formal distribution that monolithic anode filter plate replaces like this with " male-female-the moon ", the electrofiltration plate fixing by back up pad is put into reactor draw-in groove fixing, then electrofiltration plate is connected with voltage stabilized source, adopt pulsed voltage, control voltage swing is 8.0V, electrofiltration distance between plates is 40 mm, and after switching on power, the series reaction such as electrocatalysis, micro-electrolysis, electricity flocculation will occur electrofiltration plate.
Petroleum wastewater is put into reactor 2 through water-in 1, and the water surface slightly exceeds ultrasonic transducer height and covers electrofiltration plate.Open the aerating apparatus of reactor bottom, controlling aeration rate is 200 Lh
-1.Open ultrasonic generator and voltage stabilized source switch, petroleum wastewater, after collaborative supersound process 120 min of electrofiltration plate, enters next flow process by water outlet 10 and further carries out biochemical treatment; COD in the former water of petroleum wastewater
crconcentration is 18000 mg/L, after treatment, and COD in water outlet
crconcentration is less than 1600 mg/L.
Embodiment 4: this electrofiltration plate is the integrated filter plate of anode and cathode, and it comprises electrocatalysis cathode material, electrocatalysis anode material and micro-electrolysis material, and wherein cathodic electricity catalytic material is graphite, and anode electrocatalysis material is titanium magnesium alloy, and it is tabular that structure is porous; Electrofiltration plate thickness is 40 mm, and electrocatalysis cathode material and electrocatalysis anode material are pressed into after tabular and are distributed in micro-electrolysis material both sides.Micro-electrolysis material is mixed according to volume ratio 1.2:1 ratio by aluminium-carbon, it is shaped as unsetting particle, particle size range is 100 orders, in micro-electrolysis material, increasing volume ratio and be 0.3% copper scale (particle diameter is 60 orders) increases the potential difference of filler, add auxiliary material polyethylene hollow plastic pellet, hollow ball diameter be 38 mm(Fig. 3 a).
The integrated filter plate of anode and cathode in the present embodiment is applied to process in high concentrated organic wastewater device, this device comprises reactor 2, power supply 3, time switch 4, the integrated filter plate 18 of anode and cathode, pneumatic pump 9, aeration tube 13, ultrasonic transducer 11, ultrasonic generator 12, the integrated filter plate 18 of anode and cathode is arranged in reactor 2 by draw-in groove, the integrated filter plate 18 of anode and cathode is connected with power supply 3 by time switch 4, aeration tube 13 is arranged on reactor 2 bottoms, aeration tube 13 is connected with pneumatic pump 9 by under meter 7, 9 of under meter 7 and pneumatic pumps are provided with valve 8, on reactor 2, be provided with water-in 1 and water outlet 10, 18 ultrasonic transducers are symmetrical is respectively arranged on two the reactor walls outsides parallel with electrofiltration plate, electrofiltration plate is vertical with ultrasonic propagation direction, the ultrasonic transducer (see figure 5) that is connected with ultrasonic generator,
Reactor is stainless steel reactor, and the opposite face welding ultrasonic transducer at reactor, forms parallel plate type ultrasonic reactor, and be connected with ultrasonic generator, guarantees that operating power and frequency adapt.Ultrasonic generator operating frequency and power are respectively 68 kHz and 2700 W.Ultrasonic transducer distribution triangular in shape, interval 400 mm between two ultrasonic transducers, the ultrasonic transducer on corresponding surface becomes corresponding distribution, and the spacing between two outer walls of installation 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 fixing by back up pad is put into reactor draw-in groove fixing, then electrofiltration plate is connected with voltage stabilized source, adopt pulsed voltage, control voltage swing is 8.0V, electrofiltration distance between plates is 80 mm, by the integrated filter plate series arrangement of polylith anode and cathode, after switching on power, will there is the series reaction such as electrocatalysis, micro-electrolysis, electricity flocculation in electrofiltration plate.
Wastewater from chemical industry is put into reactor 2 through water-in 1, and the water surface slightly exceeds ultrasonic transducer height and covers electrofiltration plate.Open the aerating apparatus of reactor bottom, controlling aeration rate is 200 Lh
-1.Open ultrasonic generator and voltage stabilized source switch, wastewater from chemical industry, after collaborative supersound process 120 min of electrofiltration plate, enters next flow process by water outlet 10 and further carries out biochemical treatment; COD in the former water of wastewater from chemical industry
crconcentration is 16000 mg/L, after treatment, and COD in water outlet
crconcentration is less than 1200 mg/L.
Embodiment 5: this electrofiltration plate is the extremely integrated filter plate of anode filter plate regulating YIN and YANG, anode electrofiltration plate comprises anode electrocatalysis material, micro-electrolysis material and conductor material, its Anodic electrocatalysis material is the particle (particle length is 5 ~ 15 mm, and width is 3 ~ 6 mm) that the fragmentation of Ti-Ni alloy plate forms; 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 iron-carbon, and conductor material is selected copper cash, diameter is 3.0 mm, is Z-shaped and is distributed in micro-electrolysis stuffing;
The integrated filter plate of anode and cathode comprises electrocatalysis cathode material, electrocatalysis anode material and micro-electrolysis material, wherein cathodic electricity catalytic material is the particle that the fragmentation of titanium plate forms, anode electrocatalysis material is the particle that the fragmentation of titanium magnesium alloy plate forms, micro-electrolysis material is mixed according to volume ratio 1.1:1 ratio by aluminium-carbon, it is spherical that it is shaped as particle, particle size range is 40 orders, electrocatalysis cathode material and electrocatalysis anode material (mass ratio 1:1) are mixed in micro-electrolysis stuffing, and it is 1:3(Fig. 3 b with the mixing quality ratio of micro-electrolysis material).
The extremely integrated filter plate of the present embodiment Anodic filter plate regulating YIN and YANG is applied to process in high concentrated organic wastewater device, apparatus structure is with embodiment 1, and difference is that the anode filter plate of 2 series connection and the integrated filter plate of anode and cathode are alternately distributed in reactor with " sun-integrated-integrated-Yang "; Adopt the present embodiment device Treatment of Wastewater in Coking, COD in the former water of coking chemical waste water
crconcentration is 3200 mg/L, after treatment, and COD in water outlet
crconcentration is less than 800 mg/L.
Embodiment 6: this electrofiltration plate is the extremely integrated filter plate of negative electrode filter plate regulating YIN and YANG, cathodic electricity filter plate comprises cathodic electricity catalytic material, micro-electrolysis material and conductor material, wherein cathodic electricity catalytic material is titanium plate, cathodic electricity catalytic material is arranged at micro-electrolysis stuffing both sides, structure is that porous is tabular, on porous plate, aperture is 200 orders, and electrofiltration plate thickness is 10 mm.Micro-electrolysis material is mixed according to volume ratio 1:1 ratio by iron-carbon, and conductor material is selected nickel wire, and diameter is 5.0 mm, is Z-shaped and is distributed in micro-electrolysis stuffing;
The integrated filter plate of anode and cathode comprises electrocatalysis cathode material, electrocatalysis anode material and micro-electrolysis material, wherein cathodic electricity catalytic material is the particle that graphite fragmentation forms, anode electrocatalysis material is the particle that the fragmentation of Ti-Ni alloy plate forms, micro-electrolysis material is mixed according to volume ratio 1:1 ratio by aluminium-carbon, it is spherical that it is shaped as particle, particle size range is 70 orders, electrocatalysis cathode material and electrocatalysis anode material (mass ratio 2:1) are mixed in micro-electrolysis stuffing, and it is 1:1 with the mixing quality ratio of micro-electrolysis material.
The extremely integrated filter plate of negative electrode filter plate regulating YIN and YANG in the present embodiment is applied to process in high concentrated organic wastewater device, apparatus structure is with embodiment 1, and difference is that the negative electrode filter plate of 3 series connection and the integrated filter plate of anode and cathode are alternately distributed in reactor with " integrated-cloudy-integrated "; Adopt the present embodiment device to process petroleum wastewater, COD in the former water of petroleum wastewater
crconcentration is 18000 mg/L, after treatment, and COD in water outlet
crconcentration is less than 2000 mg/L.
Embodiment 7: this electrofiltration plate is negative electrode filter plate, anode filter plate, the integrated filter plate of anode and cathode, cathodic electricity filter plate comprises cathodic electricity catalytic material, micro-electrolysis material and conductor material, anode electrofiltration plate comprises anode electrocatalysis material, micro-electrolysis material and conductor material, wherein cathodic electricity catalytic material is stainless steel, anode electrocatalysis material is Ti-Ni alloy plate, it is tabular that structure is porous, and on porous plate, the aperture in hole is 100 orders; Electrofiltration plate thickness is 20 mm, and electrocatalysis material is pressed into the tabular micro-electrolysis material both sides that are distributed in; Micro-electrolysis material is mixed according to volume ratio 0.8:1 ratio by aluminium-carbon, and it is spherical that it is shaped as particle, and particle size range is 18 orders, and conductor material is selected nickel wire, and specification is 0.8 mm, S-shaped being distributed in micro-electrolysis stuffing.
The integrated filter plate of anode and cathode comprises electrocatalysis cathode material, electrocatalysis anode material and micro-electrolysis material, wherein cathodic electricity catalytic material is graphite, anode electrocatalysis material is Ti-Ni alloy plate, electrocatalysis cathode material and electrocatalysis anode material are pressed into after tabular and are distributed in micro-electrolysis material both sides, micro-electrolysis material is mixed according to volume ratio 1:1 ratio by aluminium-carbon, it is spherical that it is shaped as particle, particle size range is 70 orders, increases volume ratio and be the potential difference that 0.15% copper scale (particle diameter is 40 orders) increases filler in micro-electrolysis material.
Negative electrode filter plate, anode filter plate, the integrated filter plate of anode and cathode in the present embodiment are applied to process in high concentrated organic wastewater device, apparatus structure is with embodiment 1, and difference is that the negative electrode filter plate of 2 series connection, 2 series connection anode filter plates, the integrated filter plates of anode and cathode are alternately distributed in reactor; Adopt the present embodiment device treatment of dyeing and printing, COD in the former water of dyeing waste water
crconcentration is 13000 mg/L, after treatment, and COD in water outlet
crconcentration is less than 2400 mg/L.
Claims (10)
1. an electrofiltration plate, it is characterized in that: it is to make the integrated filter plate of anode and cathode by anode electrocatalysis material, cathodic electricity catalytic material, micro-electrolysis material, or make plate-shaped anode filter plate or negative electrode filter plate by anode electrocatalysis material or cathodic electricity catalytic material, micro-electrolysis material, electro-conductive material, anode electrocatalysis material and/or cathodic electricity catalytic 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, be pressed into tabularly, the mixing quality of electrocatalysis material and micro-electrolysis material is than being 1:1 ~ 1:3; During the integrated electrofiltration plate of preparation anode and cathode, anode electrocatalysis material is 2:1 ~ 1:1 with the mixing quality ratio of cathodic electricity catalytic material.
2. electrofiltration plate according to claim 1, it is characterized in that: cathodic electricity catalytic material is titanium, stainless steel or graphite, anode electrocatalysis material is Ti-Ni alloy, the violent alloy of titanium or titanium magnesium alloy, electrocatalysis material is porous particle tabular or that formed by porous plate shearing-crushing, on porous plate, the aperture in hole is 30 ~ 200 orders, the broken particle length forming is 5 ~ 15mm, and width is 3 ~ 6mm.
3. electrofiltration plate according to claim 1, is characterized in that: micro-electrolysis material is mixed by iron-carbon or aluminium-carbon, and its mixed volume is than being 0.8:1 ~ 1.2:1.
4. according to the plate of electrofiltration described in claim 3, it is characterized in that: micro-electrolysis material also comprises that volume percent is 0.1% ~ 0.3% copper scale or platinum bits, and copper scale or platinum bits particle diameter are 18 ~ 100 orders.
5. according to the plate of electrofiltration described in claim 3 or 4, it is characterized in that: in micro-electrolysis stuffing, also contain polyethylene hollow plastic pellet or polypropylene hollow baton round, hollow plastic pellet diameter is 5 ~ 38 mm.
6. according to the plate of electrofiltration described in claim 1, it is characterized in that: electro-conductive material is copper cash or nickel wire, copper cash or nickel wire diameter are 0.8 ~ 6.0 mm, and S-shaped, Z-shaped being distributed in micro-electrolysis material is river font distribution above if electro-conductive material is one.
7. according to the plate of electrofiltration described in claim 5, it is characterized in that: electrofiltration plate thickness is 10 ~ 50 mm.
8. right to use requires the processing high concentrated organic wastewater device of electrofiltration plate described in 1, it is characterized in that: comprise reactor (2), power supply (3), time switch (4), two blocks of above electrofiltration plates, pneumatic pump (9), ultrasonic transducer (11), ultrasonic 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 pneumatic pump (9) by under meter (7), reactor is provided with water-in and water outlet on (2), two above ultrasonic transducer (11) symmetries are arranged on two the reactor wall outsides parallel with electrofiltration plate, electrofiltration plate is vertical with ultrasonic propagation direction, ultrasonic transducer is connected with ultrasonic generator, between electrofiltration plate, 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 adopt the over-over mode of " sun-male-female-the moon " to be distributed in reactor;
B, the over-over mode by 2 ~ 4 series connection anode filter plates and 2 ~ 4 series connection negative electrode filter plates with " sun-male-female-the moon " are distributed in reactor, after setting, series connection anode filter plate and the negative electrode filter plate of connecting are coupled together again;
C, in reactor, electrofiltration plate is 1 ~ 4 series connection anode filter plate or 1 ~ 4 series connection negative electrode filter plate during with the integrated filter plate combination of more than 1 anode and cathode, and connect anode filter plate or connect negative electrode filter plate and the integrated filter plate of anode and cathode are alternately distributed in reactor;
D, in reactor, electrofiltration plate is 1 ~ 4 series connection anode filter plate, 1 ~ 4 series connection negative electrode filter plate and when more than 1 the integrated filter plate of anode and cathode combines, and the electrofiltration plate of three types is alternately distributed in reactor;
E, in reactor, electrofiltration plate is more than 1 integrated filter plate of anode and cathode, and it is connected with power supply.
9. processing high concentrated organic wastewater device according to claim 9, it is characterized in that: the ultrasonic transducer on reactor outer wall is hexagon, circle or Triangle-Profile, spacing distance between two ultrasonic transducers is 200 ~ 400 mm, and the spacing between two outer walls of installation ultrasonic transducer is 160 ~ 200 mm.
10. processing high concentrated organic wastewater device according to claim 9, is characterized in that: it is 300 ~ 2700 W that ultrasonic generator uses power, and frequency of utilization is 17 ~ 68 kHz, and electrofiltration plate impressed voltage is 0.1 ~ 8.0 V, and aeration rate scope is 70 ~ 200 Lh
-1.
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