CN104524942B - The method and apparatus that the collaborative liquid phase of electrodialysis purifies industrial SO 2 waste gas - Google Patents
The method and apparatus that the collaborative liquid phase of electrodialysis purifies industrial SO 2 waste gas Download PDFInfo
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Abstract
The invention discloses the method that the collaborative liquid phase of a kind of electrodialysis purifies industrial SO 2 waste gas, the method is by electrodialytic technique, liquid phase catalytic oxidation technology combines, it is applied to absorption and the purification of form waste gas of sulfur dioxide, form waste gas of sulfur dioxide passes into the cathode chamber using water as absorption liquid, in water, the sulphuric acid that concentration is relatively low is generated under catalyst and electrochemical synergistic oxidation effect, utilize electrodialysis effect that the dilute sulfuric acid that catalytic oxidation in cathode chamber generates is enriched to anode chamber, realize catalytic oxidation, product efficiently separate and product enrichment concentration, thus obtaining concentration to reach the concentrated sulphuric acid of Product-level requirement；The method is integrated multiple reaction in a reactor, increase liquid phase scrubbing and purify capacity and the efficiency of sulfur dioxide, shorten the technological process of gas washing in SA production, reduce and purify cost, this technology contributes to industrial waste gas recycling, can produce huge economic benefit and social benefit。
Description
Technical field
The present invention relates to a kind of method and apparatus utilizing electrodialytic technique purified treatment low-concentration sulfur dioxide industrial waste gas, belong to field of environment engineering。
Background technology
SO2It is one of common Air Pollutant Discharge, SO2Polluting and mainly caused by energy resource consumption, and economic development be unable to do without the support of the energy, China's Energy Mix is again based on coal, and the coal that combustion of sulfur amount is higher in a large number is to cause SO2The key factor of a large amount of discharges and severe contamination。" China Environmental State Bulletin " shows, from nineteen ninety, the atmospheric pollution of China big and medium-sized cities is more serious, and the atmospheric pollution of samll cities and towns also has the trend increased the weight of, and the scope of haze weather and degree all strengthen to some extent in recent years。At SO2The purified treatment aspect of gas, has carried out excessive quantity research both at home and abroad。For three types after in before the purification divided combustion of sulfur, for SO2The purification of tail gas has the methods such as solid phase absorption, liquid phase scrubbing, solid catalysis oxidation, liquid phase catalytic oxidation, electrochemically purifies SO2Research existing electron-beam desulfurization method, plasma method。In traditional catalytic oxidation process for preparing sulfuric acid, by SO2It is converted into SO3Range request of crossing complete under high temperature and catalyst exist, to SO2Gaseous oxidation energy requirement is high, and cost is also high, at liquid phase oxidation SO2Conversion energy loss can be made to be greatly lowered。
Electrodialytic technique is under the effect of DC electric field, with potential difference for motive force, utilizes the selective penetrated property of ion exchange membrane, electrolyte is separated from solution, thus realizing the purpose of the desalination of solution, concentration, refining or purification。Electrodialytic technique has many advantages, as: floor space is little, and capital expenditure is few, saves labour force, easy to maintenance, easily realizes automatization etc.；It namely unlike distillation by more than 90% water become water vapour and must consume like that a large amount of fuel, with high-pressure pump, substantial amounts of hydrone must be extruded semipermeable membrane also different from reverse osmosis, or ion exchanges such frequent regeneration, discharge acid-base waste fluid contaminated environment once again。In these areas, electrodialysis has particular advantages。
The sulfur method of the waste gas of publication number a kind of sulfur-containing oxide that has been the patent disclosure of CN1572359A and device, the method is by SO2Pass into soluble alkali solution to absorb, electrodialytic technique is then in the regenerative process absorbing liquid, technique uses many covering devices such as absorption plant, regenerating unit, circulating device, its core is absorption and the regeneration cycle that the conversion between bisulfites and sulphite constitutes desulfurization, and the vitriolated by-product of generation needs extra harmless treatment。
Publication number has been the patent disclosure of CN102008875A, and one utilizes low concentration SO2The method of flue gas during smelting, the method includes low-concentration sulfur dioxide and absorbs, absorbs rich desorbing, desorption barren solution ultrasonic electrochemical dialysis, desorption gas antacid Four processes, uses citrate to absorb rich solution and carries out desorbing, the Gaochun SO obtained2For antacid, by the method for ultrasonic electrochemical film dialysis, desorption barren solution being carried out purifying regeneration, course of reaction is SO2The improvement of the old technique of antacid double-absorption。
Summary of the invention
It is an object of the invention to provide the method that the collaborative liquid phase of a kind of electrodialysis purifies industrial SO 2 waste gas, the method is to purify, with existing sulfur dioxide double-absorption, the technique that the diverse purifying low-concentration form waste gas of sulfur dioxide of technique produces sulphuric acid, catalytic oxidation and enrichment concentration are integrated in a reactor and complete by this technique, and process conditions are gentle, technological process is simple, it is easy to industrialized production widely, reduces purification cost, decrease secondary pollution。
The method is with water for absorbing liquid, add transition metal salt as active catalyst, when voltage is 0.5～6V, the waste gas of flow velocity to be 20～5000ml/min, sulfur dioxide concentration be 50～5000ppm is passed into electrodialysis reactor, SO in the mixed flow process of solarization air cell and cathode chamber2Being absorbed and aoxidize, the sulphuric acid that the concentration of cathode chamber generation is relatively low is concentrated by ion exchange membrane entrance anode chamber under electric field action, and the sulfurous acid that part is not fully oxidized also turns to sulphuric acid at anode chamber's electrochemistry oxygen, and after process, gas is for purifying gas。
Described transition metal salt is Fe3+、Mn3+、Fe2+、Mn2+、Co2+、Ni2+、Zn2+One in salt, concentration is 0.001～1mol/L。
Described ion exchange membrane is perfluorinated sulfonic acid/manganese oxide/politef cluster ion exchange membrane, and this ion exchange membrane is prepared as follows obtaining:
(1) add the mixing of equal-volume mass percent concentration 0.1-1% surfactant solution at perfluorinated sulfonic acid solution moderate that mass percent concentration is 5%, stirring, ultrasonic so that it is uniformly distributed；
(2) by manganese oxide powder, tetraethyl orthosilicate, dehydrated alcohol and sulphuric acid be in mass ratio 0.1:1:5:0.1～0.3:2:5:0.1 ratio mixing, high-speed stirred 10～24 hours, form manganese oxide colloidal sol, this colloidal sol is added configured etc. in quality perfluorinated sulfonic acid solution, obtain perfluorinated sulfonic acid/manganese oxide solution；
(3) put into after polytetrafluoroethylporous porous membrane ethanol and deionized water being cleaned, dries in isopropanol and soak 12～24h and dry；
(4) treated polytetrafluoroethylporous porous membrane is put into perfluorinated sulfonic acid/manganese oxide solution soaking 24～48h, roll after taking-up, 120 DEG C of drying, then soak rolling more so 4～5 times repeatedly, namely obtain perfluorinated sulfonic acid/manganese oxide/politef cluster ion exchange membrane。
Described surfactant is TritonX-100。
Another object of the present invention is to provide the device of a kind of method realizing the collaborative liquid phase purification industrial SO 2 waste gas of electrodialysis, a reactor completes catalytic oxidation and enrichment concentration, this device structure is simple, easily operated control, it is possible to increase absorption efficiency, catalyst activity, sulphuric acid productivity also reduce production cost。
This device includes electrodialysis chamber 2, power supply, wherein electrodialysis chamber is cylindrical hermetic chamber, electrodialysis chamber is divided into solarization air cell of lower floor 9, middle level reative cell 14, upper strata separation chamber 20 by lower clapboard 13 and upper spacer 17, aeration sieve plate 12 is arranged on below lower clapboard 13, solarization air cell of lower floor 9 top is provided with catholyte entrance 8 and is positioned at above aeration sieve plate 12, and solarization air cell of lower floor bottom is provided with gaseous mixture entrance 11 and is positioned at below aeration sieve plate 12；Side, upper strata separation chamber 20 is provided with catholyte outlet 3, and top, upper strata separation chamber is provided with clean gas outlet 19；Positive plate, ion exchange membrane and minus plate spiral winding are in middle level reative cell 14, ion exchange membrane 5 is arranged between minus plate 4 and positive plate 6, gap between ion exchange membrane and minus plate forms cathode chamber, formation anode chamber, gap between positive plate and ion exchange membrane, lower clapboard 13 has reative cell catholyte entrance 7 and connects with cathode chamber, upper spacer 17 has reative cell catholyte outlet 15 and connects with cathode chamber, anolyte entrance 10 is separately positioned on electrodialysis chamber bottom and connects with top and with anode chamber with anolyte outlet 18, cathode column 1 is connected with minus plate 4, anode posts 16 is connected with positive plate 6, cathode column 1 is connected with power cathode, anode posts 16 is connected with positive source。
Described electrodialysis chamber is prepared by politef sheet material, and minus plate is stainless steel electrode plate, and positive plate is titanium or titanium plating metallio-oxide electrode plate。
When this device uses, the absorption liquid being sulfur dioxide with water, water adds transition metal salt catalyst, the absorption liquid configured is injected solarization air cell of lower floor from catholyte entrance 8, sulfur dioxide gas enters into and through sudden and violent air sifter plate 12 from gaseous mixture entrance 11 and is sufficiently mixed with absorbing liquid, is then entered absorption catalytic oxidation in the cathode chamber of electrodialysis chamber by catholyte entrance 7；Sulfur dioxide and water react generation sulfurous acid, generating sulphuric acid also needs use catalyst to be sulphuric acid by sulfurous acid catalytic oxidation, the catalyst of this process is transition metal salt, this catalyst is soluble in water, for sulfur dioxide, there is higher catalysis activity, and the electrochemical process regeneration that can pass through device itself uses；The sulphuric acid that catalyzed oxidation generates in the cathodic compartment passes through the ion exchange membrane with very alkaline active cation exchange groups under the effect of electric field, sulfate ion is made to be enriched with in anode chamber, the hydrogen radical ions binding that sulfate ion and anode electrolysis produce generates the sulphuric acid of high concentration, sulphuric acid is collected by anolyte outlet 18, cathode chamber absorbs liquid by reative cell catholyte outlet 15 entrance upper strata separation chamber, after purification, gas is discharged by clean gas outlet 19, absorbs liquid by catholyte outlet 3 discharge。
The two interelectrode magnitudes of voltage used in enrichment concentration process of the present invention adjust according to membrane area size and die opening, make the working current density of electrodialysis plant be maintained at 1 ~ 5A/m2。
The present invention utilizes electrodialytic technique to process form waste gas of sulfur dioxide, the absorption liquid being main sulfur dioxide with water, when sulfur dioxide is dissolved in water, absorbs and there is lower column balancing in liquid:
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；
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Sulfur dioxide is dissolved in after water different with pH, mainly exists with the form of sulphite and bisulfites, under high ph conditions (6-14), mainly exists with the form of sulphite, at low pH(1-4) under condition, mainly exist with the form of bisulfites。This technique mainly reflects at low ph conditions, so the main object of liquid phase catalytic oxidation is bisulfites。
In the selection of catalyst, will considering that catalyst allows for reaching fully high valence state to capture electronics from S (IV), then produce the medium enlivened, medium promotes again reaction。After capturing electronics due to high valence ion weakened, therefore must also have one add can mode make the ion weakened come back to high-valence state。
Experiment finds that Mn, Fe are good catalyst at a low ph, Ni and Zn is very low owing to lacking variable valence catalysis activity in weak property medium, and Cu oxidisability at a low ph is not strong, it is impossible to produce chain carrier from S (IV) species, thus show very faint catalysis activity。
Catalytic oxidation is there is under the effect of catalyst, it is sulfate radical by bisulfite catalytic oxidation, the liquid phase catalytic oxidation process of above-mentioned sulfur dioxide includes chemical absorbing and two subprocess of catalytic oxidation, and chemical absorbing is solid sulfur process, and catalytic oxidation is then sweetening process。This two-part net reaction is:
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Liquid phase scrubbing and catalytic oxidation two reflection process left-half in " invention operation principle schematic diagram ", namely complete in cathode chamber, and reaction and explanation are as shown in Figure 1。
In whole electrodialysis plant, the sulfate ion that in cathode chamber, catalyzed oxidation generates, under the effect of electric field, moves to anode chamber by ion exchange membrane, thus in anode chamber's enrichment concentration。At the sulphuric acid of the hydrogen radical ions binding generation high concentration that anode chamber's sulfate ion and anode electrolysis produce, reflect as follows:
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It addition, have part inferior sulfate radical, bisulfite also can pass through ion exchange membrane move to anode chamber, due to the Oxidation of anode, inferior sulfate radical dialysis come, bisulfite are changed into sulfate radical, then are combined generation sulphuric acid with hydrion。
The invention have the advantage that
(1) present invention can apply to the process of smeltery's sulfur-containing tail gas, power plant's sulfur-containing tail gas, Refinery Oil cracking desulfurization waste gas, the present invention can be additionally used in the acid-bearing wastewater process of refinery factory and sewage treatment plant and the Regeneration Treatment of desulfurizing agent；
(2) present invention changes the double-absorption technique in traditional sulfur dioxide acid exhaust, electrodialytic technique auxiliary liquid phase scrubbing oxidation is used to realize the enrichment concentration of the directed regulation and control of purified product, target product, not only can shortened process, and reduce purification cost；
(3) present invention have also been changed traditional electrodialysis and is served only for the application mode of water process or Regeneration Treatment, electrodialytic technique is applied to absorption and the purification of waste gas, opens the new way that toxic harmful exhaust gas absorption cleaning utilizes；
(4) in electrodialyzer, the oxygen produced in anode electrolysis process can effectively solve the problem that oxygen content in tail gas is low or oxygen solubility is not high and oxidation conversion efficiencies that is that cause is low；
(5) the anode electrochemical Oxidation of electrodialyzer can strengthen catalysis Activity and stabill in theory, it is possible to promotes that catalytically-active metals ion is converted so that catalyst regeneration to high-valence state by lower valency；
(6) reflection mild condition, can carry out at normal temperatures, and technological process is simple, and multipole film, multipole room process unit additionally can be adopted to improve efficiency。
(7) the method integrated multiple reaction in a reactor, obtaining relatively while high-concentration and low-concentration sulfur dioxide gas purifying rate, utilize liquid phase scrubbing, catalytic oxidation, electrodialysis and ion exchange, the sulfuric acid product of higher concentration can be produced simultaneously, increase liquid phase scrubbing and purify capacity and the efficiency of sulfur dioxide, shorten the technological process of gas washing in SA production, reduce and purify cost, this technology contributes to industrial waste gas recycling, can produce huge economic benefit and social benefit。
Accompanying drawing explanation
Fig. 1 is operation principle schematic diagram of the present invention；
Fig. 2 is electrodialysis plant structural representation of the present invention；
Fig. 3 is the schematic diagram of minus plate of the present invention, ion exchange membrane, positive plate spiral winding；
Fig. 4 is the process flow diagram of the present invention；
In figure: 1-cathode column；2-electrodialysis chamber；3-catholyte exports；4-minus plate；5-ion exchange membrane；6-positive plate；7-reative cell catholyte entrance；8-catholyte entrance；Solarization air cell of 9-lower floor；10-anolyte entrance；11-gaseous mixture entrance；The sudden and violent air sifter plate of 12-；13-lower clapboard；14-middle level reative cell；15-reative cell catholyte exports；16-anode posts；17-upper spacer；18-anolyte outlet；19-clean gas outlet；20-upper strata separation chamber；
SO 2 tail gas after 21-dedusting cooling, 22-air, 23-air pump, 24-air filter, 25-electromagnetic valve, 26-blender, 27-gas flow controller, 28-power-supply controller of electric, 29-electrodialysis reactor, 30-dehumidifier, 31-catholyte storage tank, 32-anolyte storage tank, 33-concentrated sulphuric acid, 34-sulfur dioxide analyzer, 35-purifies gas。
Detailed description of the invention
Below in conjunction with drawings and Examples, the present invention being described in further detail, it is necessary to explanation, these embodiments are preferably examples, are used for being further appreciated by the present invention, not limitation of the present invention。
Embodiment 1: the method and apparatus that the collaborative liquid phase of this electrodialysis purifies industrial SO 2 waste gas, particular content is as follows:
1, perfluorinated sulfonic acid/manganese oxide/politef cluster ion exchange membrane preparation process is as follows:
(1) in the perfluorinated sulfonic acid solution that mass percent concentration is 5% add equal-volume mass percent concentration 0.1% surfactant solution (TritonX-100) mixing, stirring, ultrasonic so that it is uniformly distributed；
(2) by manganese oxide powder, tetraethyl orthosilicate, dehydrated alcohol and sulphuric acid be in mass ratio 0.1:1:5:0.1 ratio mixing, high-speed stirred 10 hours, formed manganese oxide colloidal sol, by this colloidal sol add configured etc. quality perfluorinated sulfonic acid solution in, obtain perfluorinated sulfonic acid/manganese oxide solution；
(3) put into after polytetrafluoroethylporous porous membrane ethanol and deionized water being cleaned, dries in isopropanol and soak 24h and dry；
(4) polytetrafluoroethylporous porous membrane of step (3) is put into perfluorinated sulfonic acid/manganese oxide solution soaking 30h, roll after taking-up, 120 DEG C of drying, then soak rolling more so 4 times repeatedly, namely obtain perfluorinated sulfonic acid/manganese oxide/politef cluster ion exchange membrane。
2, purify the device of industrial SO 2 waste gas as the collaborative liquid phase of electrodialysis of ion exchange membrane with perfluorinated sulfonic acid/manganese oxide/politef cluster ion exchange membrane, it includes electrodialysis chamber 2, power supply, wherein electrodialysis chamber 2 is cylindrical hermetic chamber, electrodialysis chamber is divided into solarization air cell of lower floor 9 by lower clapboard 13 and upper spacer 17, middle level reative cell 14, upper strata separation chamber 20, aeration sieve plate 12 is arranged on below lower clapboard 13, solarization air cell of lower floor 9 top is provided with catholyte entrance 8 and is positioned at above aeration sieve plate 12, solarization air cell of lower floor 9 bottom is provided with gaseous mixture entrance 11 and is positioned at below aeration sieve plate 12；Side, upper strata separation chamber 20 is provided with catholyte outlet 3, and top, upper strata separation chamber 20 is provided with clean gas outlet 19；Positive plate 6, ion exchange membrane 5 and minus plate 4 spiral winding are in middle level reative cell 14, ion exchange membrane 5 is arranged between minus plate 4 and positive plate 6, gap between ion exchange membrane and minus plate forms cathode chamber, formation anode chamber, gap between positive plate and ion exchange membrane, lower clapboard 13 has reative cell catholyte entrance 7 and connects with cathode chamber, upper spacer 17 has reative cell catholyte outlet 15 and connects with cathode chamber, anolyte entrance 10 is separately positioned on electrodialysis chamber bottom and connects with top and with anode chamber with anolyte outlet 18, cathode column 1 is connected with minus plate 4, anode posts 16 is connected with positive plate 6, cathode column 1, anode posts 16 is connected with power supply respectively, this electrodialysis chamber and upper lower clapboard all adopt politef sheet material to prepare, acid-alkali-corrosive-resisting is good, minus plate is stainless steel electrode plate, positive plate is the Ti electrode plate being not easily corroded and having sulfur dioxide catalysis activity。(see Fig. 2-3)。
3, this device is at room temperature, using electrical conductivity (25 DEG C) less than 5mS/m, pH value be 6.8 pure water as absorb liquid, add manganese oxide as active catalyst, water and catalyst 20:1 in mass ratio are configured to process the absorption liquid of low concentration sulphur dioxide flue gas, it is directly placed into the cathode chamber of electrodialyzer, when voltage is 1V, the waste gas of flow velocity to be 500ml/min, sulfur dioxide concentration be 1000ppm is passed into electrodialysis reactor, SO in the mixed flow process of solarization air cell and cathode chamber2Being absorbed and aoxidize, the sulphuric acid that the concentration of cathode chamber generation is relatively low is concentrated by ion exchange membrane entrance anode chamber under electric field action, and the sulfurous acid that part is not fully oxidized also turns to sulphuric acid at anode chamber's electrochemistry oxygen, and after process, gas is for purifying gas。
The electrodialysis process flow chart of the purifying low-concentration industrial SO 2 waste gas shown in Fig. 4, use said apparatus, main component in flue gas: pumped by air pump 23 by air filter 24 with air 22(air 22 after the SO 2 tail gas 21 dedusting cooling that burning produces) control each gas componant with gas flow controller 27 by electromagnetic valve 25, blender 26 is formed simulated flue gas, absorption liquid in catholyte storage tank 31 is injected solarization air cell of lower floor 9 from catholyte entrance 8, waste gas is entered solarization air cell of lower floor 9 from the gaseous mixture entrance 11 of electrodialysis reactor 29 and is sufficiently mixed with absorbing liquid by sudden and violent air sifter plate 12, then absorption catalytic oxidation in the cathode chamber of electrodialysis chamber is entered by catholyte entrance 7；Absorb liquid and mix acceleration reaction at the minus plate of winding with constantly rotating between ion exchange membrane, the sulfate radical generated and part sulfurous root, minus plate 4 is connected with the cathode column 1 towards external power supply controller 28, positive plate 6 is connected with the anode posts 16 towards external power supply controller 28, the anion that reaction generates enters anode chamber by ion exchange membrane 5 under the electric field action between minus plate 4 and positive plate 6, the dilute sulfuric acid not up to concentration requirement of the water injected by anolyte entrance 10 or circulation is had in anode chamber, sulfate ion is made to be enriched with in anode chamber, the inferior sulfate radical of the non-complete oxidation permeated from ion exchange membrane 5 is further oxidized to sulfate radical by the oxygen that positive plate 6 electrolysis produces, the hydrogen radical ions binding that sulfate ion and anode electrolysis produce generates the sulphuric acid of high concentration, sulphuric acid is drawn in anolyte storage tank 32 homogenizing by anolyte outlet 18 and becomes final finished sulphuric acid 33 after inspection；After the catalyzed oxidation of cathode chamber and electrodialysis are reacted, other gas componant remaining exports 15 entrance upper strata separation chambers 20 by reative cell catholyte under the carrying of catholyte, after purification gas 35 by clean gas outlet 19 enter dehumidifier 30 dehumidify, sulfur dioxide analyzer 34 analyze detection up to standard after emptying, the absorption liquid after degassed is back to catholyte storage tank 31 is continued cycling through use by catholyte outlet 3。
In low-concentration sulfur dioxide absorption process, two interpolar electric current densities are maintained at 3A/m2。Starting to process in 10-100 hour, in exit gas, the concentration of sulfur dioxide keeps below 100ppm；After processing 8 hours, in anolyte storage tank, sulfuric acid concentration rises to 10%, and after processing 24 hours, in anolyte storage tank, sulfuric acid concentration rises to 30%, reaches sulphuric acid reuse concentration requirement。
Embodiment 2: the method and apparatus that the collaborative liquid phase of this electrodialysis purifies industrial SO 2 waste gas, particular content is as follows:
1, perfluorinated sulfonic acid/manganese oxide/politef cluster ion exchange membrane preparation process is as follows:
(1) in the perfluorinated sulfonic acid solution that mass percent concentration is 5% add equal-volume mass percent concentration 0.5% surfactant solution (TritonX-100) mixing, stirring, ultrasonic so that it is uniformly distributed；
(2) by manganese oxide powder, tetraethyl orthosilicate, dehydrated alcohol and sulphuric acid be in mass ratio 0.2:2:5:0.1 ratio mixing, high-speed stirred 15 hours, formed manganese oxide colloidal sol, by this colloidal sol add configured etc. quality perfluorinated sulfonic acid solution in, obtain perfluorinated sulfonic acid/manganese oxide solution；
(3) put into after polytetrafluoroethylporous porous membrane ethanol and deionized water being cleaned, dries in isopropanol and soak 15h and dry；
(4) polytetrafluoroethylporous porous membrane of step (3) is put into perfluorinated sulfonic acid/manganese oxide solution soaking 48h, roll after taking-up, 120 DEG C of drying, then soak rolling more so 4 times repeatedly, namely obtain perfluorinated sulfonic acid/manganese oxide/politef cluster ion exchange membrane。
2, using perfluorinated sulfonic acid/manganese oxide/politef cluster ion exchange membrane as the device of the collaborative liquid phase purification industrial SO 2 waste gas of electrodialysis of ion exchange membrane, structure is with embodiment 1, and difference is in that positive plate is titanium plating metallio-oxide electrode plate。
3, this device is at room temperature, using electrical conductivity (25 DEG C) less than 1mS/m solution pH value be 7 water as absorb liquid, add manganese sulfate as active catalyst, water and catalyst 10:1 in mass ratio are configured to process the absorption liquid of low concentration sulphur dioxide flue gas, it is directly placed into the cathode chamber of electrodialyzer, when voltage is 4V, the waste gas of flow velocity to be 1000ml/min, sulfur dioxide concentration be 5000ppm is passed into electrodialysis reactor, SO in the mixed flow process of solarization air cell and cathode chamber2Absorbed and aoxidized, the sulphuric acid that the concentration of cathode chamber generation is relatively low is concentrated by ion exchange membrane entrance anode chamber under electric field action, the sulfurous acid that part is not fully oxidized also turns to sulphuric acid at anode chamber's electrochemistry oxygen, after process gas for purify gas, after purification in gas the concentration of sulfur dioxide lower than 200ppm。
In low-concentration sulfur dioxide absorption process, two interpolar electric current densities are maintained at 4A/m2, after electrochemical ion film dialysis, absorbing sulfate concentration in liquid and reduce, the lean solution after dialysis is back to purification absorption process, and what make reactor absorbs the liquid continuing purge ability to sulfur dioxide。Sulfuric acid concentration in electrodialyzer anolyte storage tank increases with the passage of dialysis time, and after persistently processing 24 hours, the sulfuric acid concentration in anolyte storage tank can reach 40%。
Embodiment 3: the method and apparatus that the collaborative liquid phase of this electrodialysis purifies industrial SO 2 waste gas, particular content is as follows:
1, perfluorinated sulfonic acid/manganese oxide/politef cluster ion exchange membrane preparation process is as follows:
(1) in the perfluorinated sulfonic acid solution that mass percent concentration is 5% add equal-volume mass percent concentration 1% surfactant solution (TritonX-100) mixing, stirring, ultrasonic so that it is uniformly distributed；
(2) by manganese oxide powder, tetraethyl orthosilicate, dehydrated alcohol and sulphuric acid be in mass ratio 0.3:1.5:5:0.1 ratio mixing, high-speed stirred 24 hours, formed manganese oxide colloidal sol, by this colloidal sol add configured etc. quality perfluorinated sulfonic acid solution in, obtain perfluorinated sulfonic acid/manganese oxide solution；
(3) put into after polytetrafluoroethylporous porous membrane ethanol and deionized water being cleaned, dries in isopropanol and soak 24 hours and dry；
(4) polytetrafluoroethylporous porous membrane of step (3) is put into perfluorinated sulfonic acid/manganese oxide solution soaking 24h, roll after taking-up, 120 DEG C of drying, then soak rolling more so 5 times repeatedly, namely obtain perfluorinated sulfonic acid/manganese oxide/politef cluster ion exchange membrane。
2, using perfluorinated sulfonic acid/manganese oxide/politef cluster ion exchange membrane as the device of the collaborative liquid phase purification industrial SO 2 waste gas of electrodialysis of ion exchange membrane, structure is with embodiment 1；
3, this device is at room temperature, using electrical conductivity (25 DEG C) less than 1mS/m solution pH value be 7 water as absorb liquid, add ferrous sulfate as active catalyst, water and catalyst 10:1 in mass ratio are configured to process the absorption liquid of low concentration sulphur dioxide flue gas, it is directly placed into the cathode chamber of electrodialyzer, when voltage is 2V, the waste gas of flow velocity to be 5000ml/min, sulfur dioxide concentration be 2000ppm is passed into electrodialysis reactor, SO in the mixed flow process of solarization air cell and cathode chamber2Being absorbed and aoxidize, the sulphuric acid that the concentration of cathode chamber generation is relatively low is concentrated by ion exchange membrane entrance anode chamber under electric field action, and the sulfurous acid that part is not fully oxidized also turns to sulphuric acid at anode chamber's electrochemistry oxygen, and after process, gas is for purifying gas。
In low-concentration sulfur dioxide absorption process, two interpolar electric current densities are maintained at 5A/m2, flue gas after purification is discharged from absorption tower clean gas outlet, persistently keeps in exit gas the concentration of sulfur dioxide lower than 150ppm；After electrochemical ion film dialysis, absorbing sulfate concentration in liquid and reduce, the lean solution after dialysis is back to purification absorption process, and what make reactor absorbs the liquid continuing purge ability to sulfur dioxide。Sulfuric acid concentration in electrodialyzer anolyte storage tank increases with the passage of dialysis time, and after persistently processing 24 hours, the sulfuric acid concentration in anolyte storage tank can reach 40%。
In the reactor starting stage, water sulfur dioxide absorption generates sulfurous acid, and the oxidized manganese catalytic oxidation of sulfurous acid is sulphuric acid, when reaction starts to raise close to saturated i.e. absorption tower outlet sulfur dioxide concentration, after being generally reaction 120 minutes, power-on carries out dialysis, opens anolyte circulation simultaneously。
After electrodialysis is reacted, absorb sulfate radical in liquid and move to anode chamber by ion exchange membrane, absorbing liquid concentration in cathode chamber to reduce, the absorption liquid after dialysis is back to purification process, absorbs liquid with electrodialyzer circular regeneration so that absorbing the absorbability that sulfur dioxide is kept lasting by liquid。In the anode compartment, incipient stage, the sulfuric acid concentration of anolyte increases with the passage of dialysis time, after processing 24 hours, sulfuric acid concentration in anolyte can reach 40%, now in anolyte storage tank 32, with 1L/min flow velocity can be slowly injected into pure water so that sulfuric acid concentration is stable 40% after dialysis, namely can the speed of 1L/min to produce concentration be the sulphuric acid of 40%。
Claims (4)
1. the method that the collaborative liquid phase of electrodialysis purifies industrial SO 2 waste gas, it is characterised in that: with water for absorbing liquid, add transition metal salt as active catalyst, when voltage is 0.5～6V, be 20～5000mL/min, SO by flow velocity2The waste gas that concentration is 50～5000ppm passes into electrodialysis reactor, SO in the mixed flow process of solarization air cell and cathode chamber2Absorbed and aoxidized, the sulphuric acid that the concentration of generation is relatively low is concentrated by cathode chamber entrance anode chamber by ion exchange membrane under electric field action, the sulfurous acid that is not fully oxidized of part is electrochemically oxidized as sulphuric acid also into anode chamber, and after process, gas is for purifying gas；
Described transition metal salt is Fe3+、Mn3+、Fe2+、Mn2+、Co2+、Ni2+、Zn2+One in salt, concentration is 0.001～1mol/L；
Above-mentioned ion exchange membrane is perfluorinated sulfonic acid/manganese oxide/politef cluster ion exchange membrane, and this ion exchange membrane is prepared as follows obtaining:
(1) in the perfluorinated sulfonic acid solution that mass percent concentration is 5% add equal-volume mass percent concentration 0.1～1% surfactant solution mixing, stirring, ultrasonic so that it is uniformly distributed；
(2) by manganese oxide powder, tetraethyl orthosilicate, dehydrated alcohol and sulphuric acid be in mass ratio 0.1:1:5:0.1～0.3:2:5:0.1 ratio mixing, high-speed stirred 10～24 hours, form manganese oxide colloidal sol, by this colloidal sol add configured etc. quality perfluorinated sulfonic acid solution in, obtain perfluorinated sulfonic acid/manganese oxide solution；
(3) put into after polytetrafluoroethylporous porous membrane ethanol and deionized water being cleaned, dries in isopropanol and soak 12～24h and dry；
(4) polytetrafluoroethylporous porous membrane of step (3) is put into perfluorinated sulfonic acid/manganese oxide solution soaking 24～48h, roll after taking-up, 120 DEG C of drying, then soak rolling more so 4～5 times repeatedly, namely obtain perfluorinated sulfonic acid/manganese oxide/politef cluster ion exchange membrane。
2. the method that the collaborative liquid phase of electrodialysis according to claim 1 purifies industrial SO 2 waste gas, it is characterised in that: surfactant is TritonX-100。
3. realize the device that the collaborative liquid phase of the electrodialysis described in claim 1 purifies the method for industrial SO 2 waste gas, it is characterized in that: it includes electrodialysis chamber, power supply, wherein electrodialysis chamber is cylindrical hermetic chamber, electrodialysis chamber is divided into solarization air cell of lower floor (9) by lower clapboard (13) and upper spacer (17), middle level reative cell (14), upper strata separation chamber (20), aeration sieve plate (12) is arranged on lower clapboard (13) lower section, solarization air cell of lower floor top is provided with catholyte entrance (8) and is positioned at aeration sieve plate (12) top, solarization air cell of lower floor bottom is provided with gaseous mixture entrance (11) and is positioned at aeration sieve plate (12) lower section；Side, upper strata separation chamber is provided with catholyte outlet (3), and top, upper strata separation chamber is provided with clean gas outlet (19)；Positive plate (6), ion exchange membrane (5) and minus plate (4) spiral winding are in the reative cell of middle level, ion exchange membrane (5) is arranged between minus plate (4) and positive plate (6), gap between ion exchange membrane and minus plate forms cathode chamber, formation anode chamber, gap between positive plate and ion exchange membrane, lower clapboard (13) has reative cell catholyte entrance (7) and connects with cathode chamber, upper spacer (17) has reative cell catholyte outlet (15) and connects with cathode chamber, anolyte entrance (10) is separately positioned on electrodialysis chamber bottom and connects with top and with anode chamber with anolyte outlet (18), cathode column (1) is connected with minus plate (4), anode posts (16) is connected with positive plate (6), cathode column (1) is connected with power cathode, anode posts (16) is connected with positive source。
4. device according to claim 3, it is characterised in that: minus plate is stainless steel electrode plate, and positive plate is titanium or titanium plating metallio-oxide electrode plate。
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