CN104176797A - Low-energy-consumption electrochemical treatment device and method for degradation-resistant organic wastewater - Google Patents
Low-energy-consumption electrochemical treatment device and method for degradation-resistant organic wastewater Download PDFInfo
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- CN104176797A CN104176797A CN201410459856.5A CN201410459856A CN104176797A CN 104176797 A CN104176797 A CN 104176797A CN 201410459856 A CN201410459856 A CN 201410459856A CN 104176797 A CN104176797 A CN 104176797A
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Abstract
The invention relates to an electrochemical treatment device and method for degradation-resistant organic wastewater, and designs a'zero polar distance' SPE (Solid Polymer Electrolysis) electrooxidation sewage treatment electrolytic bath like a solid polymer electrolyte fuel cell technology. According to the device, an anode chamber and a cathode chamber are separated by utilizing an ion exchange membrane, the anode with stable titanium-based size, the ion exchange membrane and the nickel cathode are pressed by utilizing an end plate, and a'zero polar distance' SPE electrooxidation sewage treatment electrolytic bath is formed. When the device is subjected to electrolytic operation, the wastewater is electrically oxidized at the anode, so that organic matters and ammonia nitrogen in the water are mineralized and degraded; and running water or the wastewater is introduced into the cathode chamber, and hydrogen separated out due to electrolysis at the cathode is recovered. The device has the advantages that extra supporting electrolyte is not needed to be added, the bath pressure and energy consumption of electrooxidation can be greatly reduced due to the'zero polar distance', and the problem that oxygen (chlorine) and hydrogen separated out in the electrolysis process is solved. In addition, a carbon material is not used, reduction of current efficiency caused by carbon corrosion is avoided, and the reliability and stability of the sewage treatment device are improved. Moreover, continuous water flow is utilized at the cathode, and the scaling and plugging possibility on the cathode side of the ion exchange membrane can be greatly reduced.
Description
Technical field
The present invention relates to field of environment protection water treatment industry technical field, especially relate to a kind of organic wastewater with difficult degradation thereby apparatus for electrochemical treatment and method of less energy-consumption.
Background technology
Water pollution is increasingly extensive, and the composition of pollutent becomes increasingly complex, and character is changeable, serious threat ecotope and the mankind's health and safety.Numerous trade effluents, as coking, dyestuff, pharmacy, synthesize/papermaking of organic chemicals, iron and steel, industry waste water and the percolates such as metal processing, have toxicity high, the feature of the large and difficult for biological degradation of concentration, difficulty of governance is very large, utilizes traditional water technology to be difficult to obtain satisfied treatment effect to this type of sewage.Electrochemistry high-level oxidation technology is a kind of sewage water treatment method of green.Electrochemical oxidation utilizes the free radical (as hydroxyl radical free radical) of electrode surface generation or the oxygenant (as hypochlorous acid) generating, can the efficient oxidation degraded organic pollutants.But current electrochemical method but have problems: in water treatment procedure, the volatile quantity of waste water reaches, and obtains water rate low; Interelectrode distance is large, causes electrolyzer to be pressed high, and energy consumption is large; Simultaneously, anode and cathode can be analysed respectively chlorine and analyse oxygen and liberation of hydrogen in wastewater treatment, and mixing easily appears in two kinds of gases of traditional electrolyzer, has great potential safety hazard; In wastewater treatment process, in order to increase useless electrical conductivity of water, reduce electrolyzer and press and energy consumption, often need in waste water, add supporting electrolyte, this had both increased the reagent cost of water treatment, processed water and need continue desalination.Recently, Canada's scientific worker's PCT patent (WO2012/167375) has designed a kind of based on solid polymer electrolyte (solid polymer electrolyte, SPE) sewage processing electrolytic cell of fuel cell technology, without interpolation supporting electrolyte in the situation that, reduce significantly the groove of sewage disposal and press and energy consumption, solved the problem that the oxygen that electrolytic process is separated out, hydrogen mix.But this technology also exists problems not solve:
1. this invents the astable anode of anode of carbon/graphite base used, at long-term electro-oxidation process, comparatively serious carbon corrosion can occur, and reduces electrode life, stability and current efficiency, and has a strong impact on the sewage treating efficiency of electrolyzer;
2. need to adopt expensive Pt etc. as cathod catalyst, increase the cost of reactor;
3. electric tank cathode is gas diffusion electrode, and positively charged ion Ca very easily occurs non-water flow mistake
2+, Mg
2+deng producing alkali (as Ca (OH)
2, Mg (OH)
2deng) fouling obstruction electrode, long-time running brings the increase of cathodic polarization and energy consumption, reduces cathode life.
Summary of the invention
The organic wastewater with difficult degradation thereby apparatus for electrochemical treatment that the object of the invention is to design a kind of novel less energy-consumption, addresses the above problem.
To achieve these goals, the technical solution used in the present invention is as follows:
A kind of organic wastewater with difficult degradation thereby apparatus for electrochemical treatment of less energy-consumption, comprise pretreatment unit and SPE electrolyzer group, described SPE electrolyzer group comprises at least one SPE electrolyzer, when described SPE electrolyzer group comprises two the above SPE electrolyzers, between described SPE electrolyzer, is set up in parallel; The water-in of described pretreatment unit is communicated with pending waste water source, and the water outlet of described pretreatment unit is communicated to SPE electrolyzer described in each;
Described SPE electrolyzer comprises ion-exchange membrane and at anolyte compartment and the cathode compartment of described ion-exchange membrane both sides;
Described anolyte compartment comprises anode end plate, porous anode propping material and anode catalyst layer, a side towards described ion-exchange membrane on described anode end plate is provided with anode flow field groove, the feed-water end of described anode flow field groove is provided with anode water-in, and the water side of described anode flow field groove is provided with anode water outlet; Described anode catalyst layer and the sealing of described porous anode propping material are arranged between described anode end plate and described ion-exchange membrane; Described anode catalyst layer, between described ion-exchange membrane and described porous anode propping material, and is close on described porous anode propping material; Described porous anode propping material is provided with anode collector, and described anode collector sealing is stretched out outside described anode end plate and described ion-exchange membrane;
Described cathode compartment comprises cathode end plate and porous cathode catalytic material, a side towards described ion-exchange membrane in described cathode end plate is provided with cathode flow field groove, the feed-water end of described cathode flow field groove is provided with negative electrode water-in, and the water side of described cathode flow field groove is provided with negative electrode water outlet; Described porous cathode catalytic material sealing is arranged between described cathode end plate and described ion-exchange membrane; Described porous cathode catalytic material is provided with cathode current collector, and described cathode current collector sealing is stretched out outside described cathode end plate and described ion-exchange membrane;
The water outlet of described pretreatment unit is communicated to SPE anode electrolytic cell water-in described in each, and described in each, SPE anode electrolytic cell water outlet is communicated to processing water out;
Described in each, the negative electrode water-in of SPE electrolyzer is communicated to water source or pending waste water source from the beginning; Described in each, the negative electrode water outlet of SPE electrolyzer is communicated to and processes water water leg or be circulated to negative electrode water inlet.
Described porous anode propping material is corrosion resistant wire establishment net, and order number is 50-400 order; Diameter wiry is 10-500 micron; The thickness of described wire establishment net is 100 microns-1000 microns, described wire establishment net is porosity >40%, the expanded metal of aperture >1 micron or be the punch metal net of >1 * 2, aperture millimeter;
Described anode catalyst layer is RuO
2-TiO
2, PbO
2, SnO
2-Sb
2o
3, Nb
2o
5-SnO
2, SnO
2-In
2o
3, IrO
2-Ta
2o
5, or rare-earth oxide/Sb
2o
5-SnO
2in one or more mixture;
Described cathode end plate is that nickel or stainless steel nickel plating are made;
The design of described cathode flow field groove is consistent with described anode flow field groove, for horizontal or longitudinally snakelike, pectination groove arrange, groove width 1-3 millimeter, groove depth 0.5-2.0 millimeter, the parallel setting of two or three flow path groove, flow field conduit starts to finish to water outlet from water-in;
Described porous cathode catalytic material is the cathode for hydrogen evolution electrocatalysis material being applicable in alkaline water electrolytic cell.
Described corrosion resistant wire comprises tungsten filament, titanium silk, molybdenum filament or niobium silk; Described cathode for hydrogen evolution electrocatalysis material comprises Ni, Raney Ni, Ni-S, Ni-Mo, or Ni-Mo-S.
Described corrosion resistant wire establishment net is titanium net, and thickness is 300 microns-2000 microns; Or described corrosion resistant wire establishment net is POROUS TITANIUM PLATE or punching titanium metal net, and the thickness of described POROUS TITANIUM PLATE is 500 microns-3000 microns, and porosity is greater than 40%; The aperture of described punching titanium metal net is greater than 1 * 2 millimeter, thickness 1-2 millimeter.
Described cathode compartment is closely connected with described anolyte compartment, only by described ion-exchange membrane, is intercepted separately, and the thickness of described ion exchange membrane material is 50 microns-150 microns;
Described ion exchange membrane material is cationic exchange membrane or anion-exchange membrane.
Also comprise silicon sealing-ring, between described anode end plate and described ion-exchange membrane, by described silica gel sealing ring, seal, between described cathode end plate and described ion-exchange membrane, also by described silica gel sealing ring, seal.
An organic wastewater with difficult degradation thereby electrochemical process for treating for less energy-consumption, comprises that step is as follows:
Treatment sewage, after pretreatment technology is removed insoluble particle, without adding supporting electrolyte, enters the anolyte compartment of each SPE electrolyzer in SPE electrolyzer group continuously with fixed flow rate;
Treatment sewage in each SPE electrolyzer is with the flow velocity of 0.02-0.10 milliliter/(Ping side Li meter ˙ minute), through anode flow field concentrated flow, enter anolyte compartment, under the direct current effect that is 2-4V in external operating voltage, Organic Pollutants in Wastewater and ammonia nitrogen are at anode surface generation electrochemical oxidation, under the effect of the >1.6V of anode high oxidation electromotive force, Catalytic Layer surface produces the oxygenant that comprises hydroxyl radical free radical, ozone and chlorine, oxidative degradation Organic Pollutants in Wastewater and ammonia nitrogen;
Waste water, after anodizing is processed, goes out described anolyte compartment through described anode flow field concentrated flow;
Meanwhile, adopt tap water continuous circulation to enter cathode compartment, catholyte produces hydrogen and takes cathode compartment out of with negative electrode current; Negative electrode water is regularly with part of running water or the former water displacement of pre-treatment.
Described treatment sewage comprises coking, printing and dyeing, chemical industry or food service industry waste water and percolate;
Described pretreatment technology comprises coagulation and precipitation;
Catalytic Layer surface produces oxygenant and comprises hydroxyl radical free radical and chlorine.
The so-called SPE of the present invention, i.e. solid polymer electrolyte, solid polymer electrolyte.
The object of patent of the present invention is to overcome deficiency of the prior art, thereby provide a kind of difficult degradation sewage electrochemical process for treating and device of new and effective less energy-consumption, reduce difficult processing cost of falling organic sewage, improve the reliability and stability of waste disposal plant.
Beneficial effect of the present invention can be summarized as follows:
1) waste disposal plant in the present invention avoids using carbon material completely, can avoid corroding due to carbon material the decline of the sewage treating efficiency causing, the decline of current efficiency, the reliability and stability of raising waste disposal plant;
2) in the present invention, adopt Ni net to replace the noble metal catalysts such as Pt of negative electrode in SPE electrolyzer, with Ti cardinal extremity plate, replace graphite end plate etc., can significantly reduce the cost of waste disposal plant;
3) negative electrode is introduced current, has slowed down greatly the scale formation of ion-exchange membrane cathode side, the problem of having avoided negative electrode to stop up, the stability of raising waste disposal plant;
4) in the present invention, in sewage treatment tank heap, adopted the difference water intake mode of single electrolyzer, the mode of difference water outlet, if the advantage of this water distribution manner is that in treatment trough heap, certain electrolyzer goes wrong, only need stop supplying water to the electrolyzer going wrong, and the direct short circuit of the positive and negative electrode of this electrolyzer can be guaranteed to the normal operation of other electrolyzers of this electrolyzer heap, without dismantling whole electrolyzer because of the problem of certain electrolyzer, thus sewage treatment capacity and the efficiency of raising electrolyzer.
Accompanying drawing explanation
Fig. 1. organic waste water is electrochemical treatment schema in SPE electrolyzer;
Wherein, 301. pre-treatment; 302.SPE electrolyzer (heap); 311. water inlet; 312. water outlet; 313. pretreatment unit residues.
Fig. 2 is the structural representation of the main apparent direction of SPE electrooxidation system of the present invention;
Fig. 3 is the stretch-out view of SPE electrooxidation system of the present invention.
Wherein: 1. anode end plate, 2. anode flow field groove; 3. silica gel sealing ring; 4. porous anode propping material; 5. anode catalyst layer; 6. anode collector; 7. ion-exchange membrane; 8. cathode current collector; 9. porous cathode catalytic material; 10. cathode flow field; 11. cathode end plate; 101. anode water inlets (waste water); 102. anode water outlets (processing water); 201. negative electrode water inlets (tap water); 202. negative electrode water outlets.
Embodiment
In order to make technical problem solved by the invention, technical scheme and beneficial effect clearer, below in conjunction with drawings and Examples, the present invention is further elaborated.Should be appreciated that specific embodiment described herein, only in order to explain the present invention, is not intended to limit the present invention.
The organic wastewater with difficult degradation thereby apparatus for electrochemical treatment of a kind of less energy-consumption as shown in Figure 1 to Figure 3, comprise pretreatment unit 301 and SPE electrolyzer group, described SPE electrolyzer group comprises at least one SPE electrolyzer 302, when described SPE electrolyzer group comprises two the above SPE electrolyzers 302, between described SPE electrolyzer 302, be set up in parallel; The water-in of described pretreatment unit 301 is communicated with pending waste water source, and the water outlet of described pretreatment unit 301 is communicated to SPE electrolyzer 302 described in each; Described SPE electrolyzer 302 comprises ion-exchange membrane 7 and at anolyte compartment and the cathode compartment of described ion-exchange membrane 7 both sides; Described anolyte compartment comprises anode end plate 1, porous anode propping material 4 and anode catalyst layer 5, a side towards described ion-exchange membrane 7 on described anode end plate 1 is provided with anode flow field groove 2, the feed-water end of described anode flow field groove 2 is provided with anode water-in 101, and the water side of described anode flow field groove 2 is provided with anode water outlet 102; Described anode catalyst layer 5 and 4 sealings of described porous anode propping material are arranged between described anode end plate 1 and described ion-exchange membrane 7; Described anode catalyst layer 5, between described ion-exchange membrane 7 and described porous anode propping material 4, and is close on described porous anode propping material 4; Described porous anode propping material 4 is provided with anode collector 6, and described anode collector 6 sealings are stretched out outside described anode end plate 1 and described ion-exchange membrane 7; Described cathode compartment comprises cathode end plate 11 and porous cathode catalytic material 9, a side towards described ion-exchange membrane 7 in described cathode end plate 11 is provided with cathode flow field 10 grooves, the feed-water end of described cathode flow field 10 grooves is provided with negative electrode water-in 201, and the water side of described cathode flow field 10 grooves is provided with negative electrode water outlet 202; Described porous cathode catalytic material 9 sealings are arranged between described cathode end plate 11 and described ion-exchange membrane 7; Described porous cathode catalytic material 9 is provided with cathode current collector 8, and described cathode current collector 8 sealings are stretched out outside described cathode end plate 11 and described ion-exchange membrane 7; The water outlet of described pretreatment unit 301 is communicated to SPE electrolyzer 302 anode water-ins 101 described in each, and described in each, SPE electrolyzer 302 anode water outlets 102 are communicated to processing water out; Described in each, the negative electrode water-in 201 of SPE electrolyzer 302 is communicated to water source or pending waste water source from the beginning; Described in each, the negative electrode water outlet 202 of SPE electrolyzer 302 is communicated to and processes water water leg or be circulated to negative electrode water-in 201.
In the embodiment being more preferably, described porous anode propping material is corrosion resistant wire establishment net (order number is 50-400 order), expanded metal (porosity >40%, aperture >1 micron) or punch metal net (>1 * 2 millimeter, aperture); Described anode catalyst layer 5 is RuO
2-TiO
2, PbO
2, SnO
2-Sb
2o
3, Nb
2o
5-SnO
2, SnO
2-In
2o
3, IrO
2-Ta
2o
5, or rare-earth oxide/Sb
2o
5-SnO
2in one or more mixture; Described cathode end plate 11 is made for nickel or stainless steel nickel plating; Described cathode flow field 10 groove designs are consistent with described anode flow field groove 2, for horizontal or longitudinal snakelike, Shu Installed groove is arranged, groove width 1-3 millimeter, groove depth 0.5-2.0 millimeter, two or three flow path groove is parallel to be set to horizontal or longitudinal snakelike groove and to arrange, and flow field conduit starts to finish to water outlet from water-in; Described porous cathode catalytic material 9 is for being applicable to the cathode for hydrogen evolution electrocatalysis material in alkaline water electrolytic cell.
In the embodiment being more preferably, described corrosion resistant wire comprises tungsten filament, titanium silk, molybdenum filament or niobium silk; Described cathode for hydrogen evolution electrocatalysis material comprises Ni, Raney Ni, Ni-S, Ni-Mo, or Ni-Mo-S.
In the embodiment being more preferably, described corrosion resistant wire establishment net is titanium net (thickness is 300 microns-2000 microns); Or described corrosion resistant wire establishment net is POROUS TITANIUM PLATE, and the thickness of described POROUS TITANIUM PLATE is 500 microns-3000 microns, and porosity is greater than 40%.Punching titanium metal net (aperture is greater than 1 * 2 millimeter, thickness 1-2 millimeter).
In the embodiment being more preferably, described cathode compartment is closely connected with described anolyte compartment, only by described ion-exchange membrane 7, is intercepted separately, and the thickness of described ion-exchange membrane 7 materials is 50 microns-150 microns; Described ion-exchange membrane 7 materials are cationic exchange membrane 7 or anion-exchange membrane 7.
In the embodiment being more preferably, the organic wastewater with difficult degradation thereby apparatus for electrochemical treatment of described less energy-consumption also comprises silicon sealing-ring, between described anode end plate 1 and described ion-exchange membrane 7, by described silica gel sealing ring 3 sealings, between described cathode end plate 11 and described ion-exchange membrane 7, also by described silica gel sealing ring 3, seal.
An organic wastewater with difficult degradation thereby electrochemical process for treating for less energy-consumption, comprises that step is as follows:
Treatment sewage, after pretreatment technology is removed insoluble particle, without adding supporting electrolyte, enters the anolyte compartment of each SPE electrolyzer 302 in SPE electrolyzer group continuously with fixed flow rate;
Treatment sewage in each SPE electrolyzer 302 is with the flow velocity of 0.02-0.10 milliliter/square centimeter minute, through anode flow field groove 2, flow into anolyte compartment, under the direct current effect that is 2-4V in external operating voltage, Organic Pollutants in Wastewater and ammonia nitrogen are at anode surface generation electrochemical oxidation, under the effect of the >1.6V of anode high oxidation electromotive force, Catalytic Layer surface produces the oxygenant that comprises hydroxyl radical free radical and chlorine, oxidative degradation Organic Pollutants in Wastewater and ammonia nitrogen;
Waste water, after anodizing is processed, flows out described anolyte compartment through described anode flow field groove 2;
Meanwhile, adopt tap water (or pretreated waste water) continuous circulation to enter cathode compartment, catholyte produces hydrogen and takes cathode compartment out of with negative electrode current; Negative electrode water is regularly with part of running water or pretreated waste water displacement.
In the embodiment being more preferably, described treatment sewage comprises coking, printing and dyeing, chemical industry or food service industry waste water and percolate; Described pretreatment technology comprises coagulation and precipitation; Catalytic Layer surface produces oxygenant and comprises hydroxyl radical free radical, ozone and chlorine etc.
In certain preferred embodiment:
1) sewage (comprising the industry waste water such as coking, printing and dyeing, chemical industry, food and percolate etc.) is after the pretreatment technology such as coagulation, precipitation are removed insoluble particle, without adding supporting electrolyte, with fixed flow rate, enter continuously " zero spacing " electrolyzer Anodic chamber;
2) waste water flows into anolyte compartment with certain flow velocity (0.02-0.20 milliliter/square centimeter minute) through anode flow field board, under the direct current effect that is 2-4V in external operating voltage, organism in waste water (and ammonia nitrogen) is at anode surface generation electrochemical oxidation, under high oxidation electromotive force (>1.6V) effect of anode, Catalytic Layer surface produces the oxygenants such as hydroxyl radical free radical, ozone and chlorine, oxidative degradation Organic Pollutants in Wastewater and ammonia nitrogen;
3) waste water, after anodizing is processed, flows out anolyte compartment through anode flow field board;
4) adopt tap water continuous circulation to enter negative electrode, catholyte produces hydrogen and takes cathode compartment out of with negative electrode current.Negative electrode water is regularly with part of running water or the former water displacement of pre-treatment.
In the middle of the present invention, " zero spacing " electrolyzer Shi You anolyte compartment, ion-exchange membrane 7 and cathode compartment form, its CONSTRUCTED SPECIFICATION as shown in Figure 2:
1) anolyte compartment is comprised of anode end plate 1, anode flow field, silica gel sealing ring 3, anode collector 6, porous anode propping material 4, anode catalyst layer 5, wherein:
I. anode end plate 1 is titanium sheet material, flow field be horizontal or longitudinally snakelike, comb Installed groove arrange, groove width 1-3 millimeter, groove depth 0.5-2.0 millimeter, two or three flow path groove is parallel to be arranged, flow field conduit starts to finish to water outlet from water-in;
Ii. porous anode propping material 4 is the corrosion resistant wire establishment such as tungsten filament, titanium silk, molybdenum filament, niobium silk net, and order number is 50-400 order, or expanded metal (porosity >40%, aperture >1 micron); Or punch metal net (>1 * 2 millimeter, aperture);
Iii. anode catalyst layer 5 is RuO
2-TiO
2, PbO
2, SnO
2-Sb
2o
3, Nb
2o
5-SnO
2, SnO
2-In
2o
3, IrO
2-Ta
2o
5, or rare-earth oxide/Sb
2o
5-SnO
2in one or more mixture;
2) negative electrode forms: porous cathode material, cathode current collector 8, cathode flow field 10, cathode end plate 11;
I. cathode end plate 11 is that the materials such as nickel or stainless steel nickel plating are made, cathode flow field 10 designs are consistent with anode flow field, for horizontal or longitudinal snakelike, Shu Installed groove is arranged, groove width 1-3 millimeter, groove depth 0.5-2.0 millimeter, two or three flow path groove is parallel to be arranged, and flow field conduit starts to finish to water outlet from water-in;
Ii. porous cathode material is the cathode for hydrogen evolution electrocatalysis material being applicable in alkaline water electrolytic cell, as Ni, and Raney Ni, Ni-S, Ni-Mo, Ni-Mo-S etc.;
3) cathode compartment of " zero spacing " electrolyzer is closely connected with anolyte compartment, only by ion-exchange membrane 7, intercepted separately, ion-exchange membrane 7 materials used are cationic exchange membrane 7 (as Nafion film) or anion-exchange membrane 7, and the thickness of film is 50-150 micron (μ m);
4) on " zero spacing " electrolyzer, the operating voltage that applies is 2-4 volt, and electric tank working current density is 1-20 milliampere/square centimeter;
5) as shown in Figure 2, have a water-in and water outlet on every pole plate, be connected separately respectively with the flow field of pole plate both sides, water-in is in pole plate bottom sides, and water outlet is on pole plate top; This design guarantees that in electrolyzer heap, each monocell cathode and anode is intake separately;
6) bipolar plate for electrolyser can be stacked to required group number, and last group cathode side is by one-sided flow-field plate, and end plate forms.
Embodiment 1
Treatment of Wastewater in Coking experiment one.
SPE electrolyzer 302 adopts Ti net (200 order) to do anode substrate, by thermolysis sintering, prepares Ti/SnO
2-Sb
2o
5solid solution anode catalyst layer 5; Adopt nickel screen as negative electrode, separate with ion-exchange membrane 7 (as Nafion) at yin, yang the two poles of the earth, and utmost point useful area is all as 200cm
2.SPE electrolyzer 302 electrooxidation Treatment of Wastewater in Coking operation scheme are as follows: coking chemical waste water enters SPE electrolyzer 302 anolyte compartments continuously with certain flow rate, and water outlet imports anode water leg; SPE electrolyzer 302 negative electrodes adopt tap water circulation, and tap water injects cathode compartment with flow velocity identical with anode, and negative electrode water outlet enters negative electrode water leg, and cathode compartment is injected in recirculation.Between SPE electrolyzer 302 cathode and anode, pass into direct current, adopt constant current charging mode operation.
When the initial COD concentration of coking chemical waste water is 280mg/L, anode flow velocity is that 4ml/min (is 0.02ml/cm
2.min), current density is made as 5mA/cm
2time, in reaction process, SPE electrolyzer 302 grooves are pressed the left and right for 3.65V, and anode effluent COD concentration is about 80mg/L, and COD degradation rate reaches 71%, and electric energy energy consumption is about 15.2kWh/m
3.
Embodiment 2
Treatment of Wastewater in Coking experiment two.
SPE electrolyzer 302 adopts Ti net (200 order) to do anode substrate, by thermolysis sintering, prepares Ti/SnO
2-Sb
2o
5solid solution anode catalyst layer 5; Adopt nickel screen as negative electrode, separate with ion-exchange membrane 7 (as Nafion) at yin, yang the two poles of the earth, and yin, yang electrode useful area is all as 200cm
2.SPE electrolyzer 302 electrooxidation Treatment of Wastewater in Coking operation scheme are identical with embodiment 1, are summarized as follows: coking chemical waste water enters SPE electrolyzer 302 anolyte compartments continuously with certain flow rate, and water outlet imports anode water leg.The electrolysis mode of negative electrode operational conditions and SPE electrolyzer 302 is consistent with embodiment 1.
When the initial COD concentration of coking chemical waste water is 280mg/L, waste water (is 0.05ml/cm with 10ml/min
2.min) flow velocity enters SPE electrolyzer 302 anodes continuously, and to set current density be 5mA/cm
2under condition, SPE electrolyzer 302 grooves are pressed the left and right for 3.65V, and anode effluent COD concentration is 160mg/L, and COD degradation rate is about 43%, and electric energy energy consumption is about 6 kWh/m
3.
Embodiment 3
Treatment of Wastewater in Coking experiment three.
SPE electrolyzer 302 adopts Ti net (200 order) to do anode substrate, by thermolysis sintering, prepares Ti/IrO
2-Ta
2o
5anode catalyst layer 5, negative electrode adopts nickel screen, and separate with ion-exchange membrane 7 (as Nafion) at yin, yang the two poles of the earth, and yin, yang electrode useful area is all 200cm
2.This experiment SPE electrolyzer 302 electrooxidation coking chemical waste waters carry out with sequence batch (, and first coking chemical waste water after SPE electrolyzer 302 anodic oxidation treatment, returns to former water water leg and mix with former water, and recirculation is injected anode and carried out electrooxidation processing.The electrolysis mode of negative electrode operational conditions and SPE electrolyzer 302 is consistent with embodiment 1.
At coking chemical waste water cumulative volume 800mL, initial COD concentration is 450mg/L, and constant current charge current density is made as 4mA/cm
2condition under, SPE electrolyzer 302 grooves are pressed the left and right for 3.2V, after reaction 4h, COD concentration is down to degradation rate and is reached 150mg/L, processing rate reaches 66.7%, energy consumption is about 12.8kWh/m
3.
More than by the detailed description of concrete and preferred embodiment the present invention; but those skilled in the art should be understood that; the present invention is not limited to the above embodiment; within the spirit and principles in the present invention all; any modification of doing, be equal to replacement etc., within protection scope of the present invention all should be included in.
Claims (8)
1. the organic wastewater with difficult degradation thereby apparatus for electrochemical treatment of a less energy-consumption, it is characterized in that: comprise pretreatment unit and SPE electrolyzer group, described SPE electrolyzer group comprises at least one SPE electrolyzer, when described SPE electrolyzer group comprises two the above SPE electrolyzers, between described SPE electrolyzer, be set up in parallel; The water-in of described pretreatment unit is communicated with pending waste water source, and the water outlet of described pretreatment unit is communicated to SPE electrolyzer described in each;
Described SPE electrolyzer comprises ion-exchange membrane and at anolyte compartment and the cathode compartment of described ion-exchange membrane both sides;
Described anolyte compartment comprises anode end plate, porous anode propping material and anode catalyst layer, on described anode end plate, a side towards described ion-exchange membrane is provided with anode flow field groove, the feed-water end of described anode flow field groove is provided with anode water-in, and the water side of described anode flow field groove is provided with anode water outlet; Described anode catalyst layer and the sealing of described porous anode propping material are arranged between described anode end plate and described ion-exchange membrane; Described anode catalyst layer, between described ion-exchange membrane and described porous anode propping material, and is close on described porous anode propping material; Described porous anode propping material is provided with anode collector, and described anode collector sealing is stretched out outside described anode end plate and described ion-exchange membrane;
Described cathode compartment comprises cathode end plate and porous cathode catalytic material, in described cathode end plate, a side towards described ion-exchange membrane is provided with cathode flow field groove, and the feed-water end of described cathode flow field groove is provided with negative electrode water-in, and the water side of described cathode flow field groove is provided with negative electrode water outlet; Described porous cathode catalytic material sealing is arranged between described cathode end plate and described ion-exchange membrane; Described porous cathode catalytic material is provided with cathode current collector, and described cathode current collector sealing is stretched out outside described cathode end plate and described ion-exchange membrane;
The water outlet of described pretreatment unit is communicated to SPE anode electrolytic cell water-in described in each, and described in each, SPE anode electrolytic cell water outlet is communicated to processing water out;
Described in each, the negative electrode water-in of SPE electrolyzer is communicated to water source or pending waste water source from the beginning; Described in each, the negative electrode water outlet of SPE electrolyzer is communicated to and processes water water leg.
2. the organic wastewater with difficult degradation thereby apparatus for electrochemical treatment of less energy-consumption according to claim 1, is characterized in that: described porous anode propping material is corrosion resistant wire establishment net, and order number is 50-400 order; Diameter wiry is 10-500 micron; The thickness of described wire establishment net is 100 microns-1000 microns, described wire establishment net is porosity >40%, the expanded metal of aperture >1 micron or be the punch metal net of >1 * 2, aperture millimeter;
Described anode catalyst layer is RuO
2-TiO
2, PbO
2, SnO
2-Sb
2o
3, Nb
2o
5-SnO
2, SnO
2-In
2o
3, IrO
2-Ta
2o
5, or rare-earth oxide/Sb
2o
5-SnO
2in one or more mixture;
Described cathode end plate is that nickel or stainless steel nickel plating are made;
The design of described cathode flow field groove is consistent with described anode flow field groove, for horizontal or longitudinally snakelike, comb Installed groove arrange, groove width 1-3 millimeter, groove depth 0.5-2.0 millimeter, the parallel setting of two or three flow path groove, flow field conduit starts to finish to water outlet from water-in;
Described porous cathode catalytic material is the cathode for hydrogen evolution electrocatalysis material being applicable in alkaline water electrolytic cell.
3. the organic wastewater with difficult degradation thereby apparatus for electrochemical treatment of less energy-consumption according to claim 2, is characterized in that: described corrosion resistant wire comprises tungsten filament, titanium silk, molybdenum filament or niobium silk; Described cathode for hydrogen evolution electrocatalysis material comprises Ni, Raney Ni, Ni-S, Ni-Mo, or Ni-Mo-S.
4. the organic wastewater with difficult degradation thereby apparatus for electrochemical treatment of less energy-consumption according to claim 2, is characterized in that: described corrosion resistant wire establishment net is titanium net, and thickness is 300 microns-2000 microns; Or described corrosion resistant wire establishment net is POROUS TITANIUM PLATE or punching titanium metal net, and the thickness of described POROUS TITANIUM PLATE is 500 microns-3000 microns, and porosity is greater than 40%; The aperture of described punching titanium metal net is greater than 1 * 2 millimeter, thickness 1-2 millimeter.
5. the organic wastewater with difficult degradation thereby apparatus for electrochemical treatment of less energy-consumption according to claim 1, it is characterized in that: described cathode compartment is closely connected with described anolyte compartment, only by described ion-exchange membrane, intercepted separately, the thickness of described ion exchange membrane material is 50 microns-150 microns;
Described ion exchange membrane material is cationic exchange membrane or anion-exchange membrane.
6. the organic wastewater with difficult degradation thereby apparatus for electrochemical treatment of less energy-consumption according to claim 1, it is characterized in that: also comprise silicon sealing-ring, between described anode end plate and described ion-exchange membrane, by described silica gel sealing ring, seal, between described cathode end plate and described ion-exchange membrane, also by described silica gel sealing ring, seal.
7. an organic wastewater with difficult degradation thereby electrochemical process for treating for less energy-consumption, is characterized in that, comprises that step is as follows:
Treatment sewage, after pretreatment technology is removed insoluble particle, without adding supporting electrolyte, enters the anolyte compartment of each SPE electrolyzer in SPE electrolyzer group continuously with fixed flow rate;
Treatment sewage in each SPE electrolyzer is with the flow velocity of 0.02-0.10 milliliter/(square centimeter minute), through anode flow field concentrated flow, enter anolyte compartment, under the direct current effect that is 2-4V in external operating voltage, Organic Pollutants in Wastewater and ammonia nitrogen are at anode surface generation electrochemical oxidation, under the effect of the >1.6V of anode high oxidation electromotive force, Catalytic Layer surface produces the oxygenant that comprises hydroxyl radical free radical and chlorine, oxidative degradation Organic Pollutants in Wastewater and ammonia nitrogen;
Waste water, after anodizing is processed, goes out described anolyte compartment through described anode flow field concentrated flow;
Meanwhile, adopt tap water continuous circulation to enter cathode compartment, catholyte produces hydrogen and takes cathode compartment out of with negative electrode current; Negative electrode water is regularly with part of running water or the former water displacement of pre-treatment.
8. the organic wastewater with difficult degradation thereby electrochemical process for treating of less energy-consumption according to claim 7, is characterized in that: described treatment sewage comprises coking, printing and dyeing, chemical industry or food service industry waste water and percolate;
Described pretreatment technology comprises coagulation and precipitation;
Catalytic Layer surface produces oxygenant and comprises hydroxyl radical free radical and chlorine.
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