CN100457234C - Waste gas treating corona discharge method and apparatus homogeneously reinforced with heterogeneous catalyst - Google Patents
Waste gas treating corona discharge method and apparatus homogeneously reinforced with heterogeneous catalyst Download PDFInfo
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- CN100457234C CN100457234C CNB2006101548199A CN200610154819A CN100457234C CN 100457234 C CN100457234 C CN 100457234C CN B2006101548199 A CNB2006101548199 A CN B2006101548199A CN 200610154819 A CN200610154819 A CN 200610154819A CN 100457234 C CN100457234 C CN 100457234C
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Abstract
The present invention discloses waste gas treating corona discharge method and apparatus homogeneously reinforced with homogeneous catalyst. The catalyst solution is first atomized in a atomizing chamber and then sprayed through the metal nozzle into the plasma corona region for homogenizing and catalyzing in the plasma reactor. Inside the corona discharging reactor, the free radical source gas molecules are excited through corona discharging to produce great amount of high activity free radicals, which produces oxidation or reduction with the pollutant gas molecule entering the reactor to degrade the pollutant. Homogenizing the catalyst can raise the efficiency of corona discharge to excite free radical, increase the yield of free radical greatly and raise the pollutant degrading efficiency obviously.
Description
Technical field
The present invention relates to waste gas processing method and device technique field, especially relate to a kind of heterogeneous catalysis homogeneous phase enhancing waste gas treating corona discharge method and device.
Background technology
In recent years, the corona discharge exhaust-gas treatment is also progressively pushed to use by extensive studies as a kind of Low Temperature Plasma Treating technology.Chemical reaction in the low temperature plasma mainly is to excite by the high energy electron that gas discharge produces to finish.Electronics, ion, free radical and excited state molecule are rich in low temperature plasma inside.Wherein inelastic collision takes place in high energy electron and gas molecule (atom), energy is converted into the interior energy of ground state molecule (atom), excite, a series of processes such as disassociation and ionization, make gas be in the state of activation, produce free radicals such as oxidisability extremely strong OH, H, O.And the nonequilibrium plasma energy consumption is not high, and this provides desirable approach for some need the removal that difficult degradation is polluted in the reaction of very big activation energy such as the atmosphere.
In order further to improve the removal efficient of plasma reaction to pollutant, a lot of researchs combine it with catalysis technique.At present, plasma catalyst and catalytic reactor are by extensive studies and exploitation, but there are very big defective in existing catalyst and reactor.Commonly used has: catalyst-supporting support is filled in the inside reactor of plasma as filler, as the dielectric of dielectric barrier discharge, strengthens plasma reaction as catalyst on the other hand on the one hand, increase reaction efficiency; Catalyst is directly loaded on the sparking electrode of plasma reactor, make it in the process that produces corona, bring into play catalytic activity; The material that will have catalytic activity loads on porous adsorbent (as active carbon, asbestos) and is filled in plasma reactor region of discharge back, makes it carry out further catalytic reaction to the pollutant of handling through exoelectrical reaction, reaches the successive stages removal.The form that catalyst exists in the method for above catalyst enhancing plasma reaction is mainly and loads on the surface of solids, and what carry out is heterogeneous catalytic reaction, and promptly solid catalyst acts on the reaction of gaseous material.Because the solid catalyst contact area is limited, this reactive mode is difficult to the reactivity of catalyst is made full use of.On the other hand,, increased filled media, increased air resistance, more restricted the disposal ability of reactor and the commercial Application of extensive big flow for the filled type reactor.
Therefore, the homogeneous phase technology of exploitation heterogeneous catalysis is applied to strengthen important technology and the means that corona discharge discharge process waste gas is breakthrough plasma reaction exhaust-gas treatment efficient.
Summary of the invention
The object of the present invention is to provide a kind of heterogeneous catalysis homogeneous phase enhancing waste gas treating corona discharge method and device, the homogeneous phase technology of heterogeneous catalysis is applied to strengthen discharge of plasma in low temperature processing waste gas, and the method can strengthen plasma reaction significantly and handle treatment of waste gas efficient.
The technical solution adopted for the present invention to solve the technical problems is:
One. heterogeneous catalysis homogeneous phase enhancing waste gas treating corona discharge method
In the catalyst spray chamber, catalyst solution is atomized, together enter the hollow nozzle corona discharge electrode of corona discharge reactor with radical source gas, and enter plasma corona district through metallic nozzle ejection, and realize the homogeneous phaseization of heterogeneous catalysis, in corona discharge reactor, bring into play catalytic action; In corona discharge reactor, excite the radical source gas molecule to produce a large amount of high mars free radicals by corona discharge, with the generation oxidation of contaminant gases molecule or the reduction reaction that enter corona discharge reactor, make pollutant obtain degraded, the heterogeneous catalysis homogeneous catalysis can strengthen the efficient that corona discharge excites radical source gas, the productive rate of free radical is increased greatly, make that the contaminant gases molecule that enters corona discharge reactor and free radical are more abundant to be contacted oxidized or be reduced, significantly improve the degradation efficiency of pollutant.
Described catalyst is the solution that class Fenton catalyst promptly contains transition metal oxide at least a in following metal ion iron, manganese, cobalt, vanadium, the copper, and solution concentration is 0.01～1.0mol/L.
Two. the device of heterogeneous catalysis homogeneous phase enhancing waste gas treating corona discharge
1) exhaust treatment system: comprise that two ends have the cylindric insulation crust of waste gas inlet and purified gas gas outlet, cylindric wire netting earthing pole, high voltage source, two insulating electrode supports and hollow nozzle corona discharge electrode; Cylindric insulation crust inwall is equipped with cylindric wire netting earthing pole, the hollow nozzle corona discharge electrode is contained in cylindric wire netting earthing pole center, and fix by the insulating electrode support at two ends, the positive pole of high voltage source connects the hollow nozzle corona discharge electrode, minus earth, described hollow nozzle corona is rotating nozzle type metal corona discharge electrode very;
2) catalyst homogeneous phase system: comprise radical source gas source, gas flowmeter, gas triple valve, steam spray chamber, catalyst spray chamber, atomized catalyst mixing chamber; The radical source gas source is successively by behind gas flowmeter and the gas triple valve, the inlet end of difference water receiving steam spray chamber and catalyst spray chamber, the inlet end of the termination atomized catalyst mixing chamber of giving vent to anger of steam spray chamber and catalyst spray chamber, the central inlet of the termination hollow nozzle corona discharge electrode of giving vent to anger of atomized catalyst mixing chamber.
Described hollow nozzle corona discharge electrode, its periphery is evenly equipped with the metallic nozzle of hollow, the metallic nozzle of hollow is connected with the hollow nozzle corona discharge electrode, the metallic nozzle of hollow the hollow nozzle corona discharge electrode radially to be the circumference equal angles uniform, axially be equidistant or many helical structures, the hollow nozzle corona discharge electrode is near the end sealing of waste gas inlet, and the hollow nozzle corona discharge electrode is near an end opening of purified gas gas outlet.
The beneficial effect that the present invention has is: heterogeneous class Fenton plasma reaction catalyst homogeneous phaseization is added in the plasma corona zone, increased the contact area of catalyst, make its degradation reaction more abundant, under the situation that does not increase corona discharge reactor internal gas flow resistance, significantly strengthen exhaust-gas treatment efficient.
Description of drawings
Fig. 1 is plasma reaction and catalyst homogeneous phase makeup interposed structure figure;
Fig. 2 is corona discharge electrode structure chart and cutaway view Amplified image;
Fig. 3 is class Fenton catalyst (Fe
2+) strengthen the plasma removal efficiency experimental result of pollutant benzene.
Among the figure: 1. cylindric insulation crust, 2. purified gas gas outlet, 3. atomized catalyst mixing chamber, 4. catalyst spray chamber, 5. steam spray chamber, 6. gas triple valve, 7. gas flowmeter, 8. radical source gas source, 9. cylindric wire netting earthing pole, 10. waste gas inlet, 11. high voltage source, 12. the insulating electrode support, 13. hollow nozzle corona discharge electrodes, the metallic nozzle of 14. hollows.
The specific embodiment
The present invention is further described below in conjunction with drawings and Examples.
As shown in Figure 1 and Figure 2, the present invention includes:
1) exhaust treatment system: comprise that two ends have the cylindric insulation crust 1 of waste gas inlet 10 and purified gas gas outlet 2, cylindric wire netting earthing pole 9, high voltage source 11, two insulating electrode supports 12 and hollow nozzle corona discharge electrodes 13; Cylindric insulation crust 1 inwall is equipped with cylindric wire netting earthing pole 9, hollow nozzle corona discharge electrode 13 is contained in cylindric wire netting earthing pole 9 centers, and it is fixing by the insulating electrode support 12 at two ends, the positive pole of high voltage source 11 connects and revolves hollow nozzle corona discharge electrode 13, minus earth, described hollow nozzle corona discharge electrode (13) are rotating nozzle type metal corona discharge electrode;
2) catalyst homogeneous phase system: comprise radical source gas source 8, gas flowmeter 7, triple valve 6, steam spray chamber 5, catalyst spray chamber 4, atomized catalyst mixing chamber 3; Hydroxyl radical gas source 8 is successively by behind gas flowmeter 7 and the gas triple valve 6, the inlet end of difference water receiving steam spray chamber 5 and catalyst spray chamber 4, the inlet end of the termination atomized catalyst mixing chamber 3 of giving vent to anger of steam spray chamber 5 and catalyst spray chamber 4, the central inlet of the termination hollow nozzle corona discharge electrode 13 of giving vent to anger of atomized catalyst mixing chamber 3.
Shown in Fig. 2 a, Fig. 2 b, described hollow nozzle corona discharge electrode 13, its periphery is evenly equipped with the metallic nozzle 14 of hollow, the metallic nozzle 14 of hollow is connected with hollow nozzle corona discharge electrode 13, the metallic nozzle 14 of hollow hollow nozzle corona discharge electrode 13 radially to be the circumference equal angles uniform, axially be equidistant or many helical structures, hollow nozzle corona discharge electrode 13 is near the end sealing of waste gas inlet 10, and hollow nozzle corona discharge electrode 13 is near an end opening of purified gas gas outlet 2.
The corona discharge plasma technology is combined with class Fenton catalytic reaction, investigate containing the benzene simulated exhaust.Configuration concentration is the solution that 0.01～1.0mol/L contains the class Fenton catalyst of ferrous ion, pack in the catalyst spray chamber 4 (as the atmospheric sampling pipe), dress water in the steam spray chamber 5, be used for regulating the humidity of radical source gas, radical source gas was divided into two-way by triple valve 6 earlier enters two spray chambers respectively before entering corona discharge reactor, regulate the gas flow that enters each spray chamber as required, because the severe impact of air-flow causes that liquid sharply shakes, bubbling, bubble constantly breaks, thereby form countless minimum drops, enter by hollow nozzle corona discharge electrode 13 1 ends with radical source gas, from 14 ejections of hollow metallic nozzle, so class Fenton catalyst enters the corona zone with air-flow.The waste gas that contains pollutant enters from corona discharge reactor one end waste gas inlet 10, the corona discharge reactor corona zone of flowing through 2 flows out from other end purified gas gas outlet, give high voltage source 11 power supplies, making the interior interpolar electric-field intensity of corona discharge reactor is 1～10kV/cm, produce the corona zone at two interpolars, because the adding of atomizing class Fenton catalyst and steam, make radical source gas cause the class Fenton's reaction, generation has strong active particles such as the hydroxyl radical free radical of strong oxidizing property, because enter the droplet size of corona zone with electrode gas minimum, has bigger effective contact area with pollutant, solid and the limited deficiency of liquid catalyst contact area have been overcome, therefore reaction is more abundant, has better removal effect.Thereby improved the removal efficiency of pollutant effectively.
Fig. 3 has reflected class Fenton catalyst (Fe
2+) strengthen the plasma removal efficiency experimental result of pollutant benzene.As can be seen from the figure, the existence of class Fenton catalyst has improved the removal efficiency of benzene effectively, and when the radical source gas humidity was 100% (RH=100%), the highest removal efficiency reached as high as 85%, has improved 25% during than no class Fenton catalyst.
The mechanism of this reaction is, under the effect of highfield, and O
2With H
2O can generate a certain amount of hydrogen peroxide, Fe
2+With Fe
3+Decompose by electronics transfer function catalyzing hydrogen peroxide, generate the hydroxyl radical free radical OH with strong oxidizing property, this process is called the class Fenton's reaction.Its key reaction is shown below:
Fe
2++H
2O
2→Fe
3++·OH
Fe
3++H
2O
2→Fe
2++HO
2·+H·
The OH free radical carries out oxidation as strong oxidizer to benzene and intermediate product thereof, finally changes into H through complex series of reactions
2O, CO
2, little molecular product such as CO, realize removing to benzene.
O
2+H
2O+e
*→O·+·OH+HO
2·+H
2O
2，etc
Fe
2++H
2O
2→Fe
3++·OH+OH
Fe
3++H
2O
2→Fe
2++HO
2·+H·
The above-mentioned specific embodiment is used for the present invention that explains, rather than limits the invention, and in the protection domain of spirit of the present invention and claim, any modification and change to the present invention makes all fall into protection scope of the present invention.
Claims (3)
1. heterogeneous catalysis homogeneous phase enhancing waste gas treating corona discharge method, in the catalyst spray chamber, catalyst solution is atomized, together enter the hollow nozzle corona discharge electrode of corona discharge reactor with radical source gas, and enter plasma corona district through metallic nozzle ejection, realize the homogeneous phaseization of heterogeneous catalysis, in corona discharge reactor, bring into play catalytic action; In corona discharge reactor, excite the radical source gas molecule to produce a large amount of high mars free radicals by corona discharge, with the generation oxidation of contaminant gases molecule or the reduction reaction that enter corona discharge reactor, make pollutant obtain degraded, the heterogeneous catalysis homogeneous catalysis can strengthen the efficient that corona discharge excites radical source gas, the productive rate of free radical is increased greatly, make that the contaminant gases molecule that enters corona discharge reactor and free radical are more abundant to be contacted oxidized or be reduced, significantly improve the degradation efficiency of pollutant; It is characterized in that: described catalyst is the solution that class Fenton catalyst promptly contains transition metal oxide at least a in following metal ion iron, manganese, cobalt, vanadium, the copper, and solution concentration is 0.01～1.0mol/L.
2. be used for the device of the heterogeneous catalysis homogeneous phase enhancing waste gas treating corona discharge of the described method of claim 1, it is characterized in that:
1) exhaust treatment system: comprise that two ends have the cylindric insulation crust (1) of waste gas inlet (10) and purified gas gas outlet (2), cylindric wire netting earthing pole (9), high voltage source (11), two insulating electrode supports (12) and hollow nozzle corona discharge electrode (13); Cylindric insulation crust (1) inwall is equipped with cylindric wire netting earthing pole (9), hollow nozzle corona discharge electrode (13) is contained in cylindric wire netting earthing pole (9) center, and it is fixing by the insulating electrode support (12) at two ends, the positive pole of high voltage source (11) connects hollow nozzle corona discharge electrode (13), minus earth, described hollow nozzle corona discharge electrode (13) are rotating nozzle type metal corona discharge electrode;
2) catalyst homogeneous phase system: comprise radical source gas source (8), gas flowmeter (7), gas triple valve (6), steam spray chamber (5), catalyst spray chamber (4), atomized catalyst mixing chamber (3); Radical source gas source (8) is successively by behind gas flowmeter (7) and the gas triple valve (6), the inlet end of difference water receiving steam spray chamber (5) and catalyst spray chamber (4), the inlet end of the termination atomized catalyst mixing chamber (3) of giving vent to anger of steam spray chamber (5) and catalyst spray chamber (4), the central inlet of the termination hollow nozzle corona discharge electrode (13) of giving vent to anger of atomized catalyst mixing chamber (3).
3. the device of heterogeneous catalysis homogeneous phase enhancing waste gas treating corona discharge according to claim 2, it is characterized in that: described hollow nozzle corona discharge electrode (13), its periphery is evenly equipped with the metallic nozzle (14) of hollow, the metallic nozzle of hollow (14) is connected with hollow nozzle corona discharge electrode (13), the metallic nozzle of hollow (14) hollow nozzle corona discharge electrode (13) radially to be the circumference equal angles uniform, axially be equidistant or many helical structures, hollow nozzle corona discharge electrode (13) is near the end sealing of waste gas inlet (10), and hollow nozzle corona discharge electrode (13) is near an end opening of purified gas gas outlet (2).
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| CN101785966B (en) * | 2010-03-02 | 2012-09-19 | 浙江菲达环保科技股份有限公司 | Method of advanced oxidation for NO in flue gas and device thereof |
| CN102527309B (en) * | 2012-01-19 | 2014-05-07 | 浙江大学 | Device and method for preparing fuel by reducing carbon dioxide by hydrogen production through vapor discharge cracking |
| CN106475029B (en) * | 2015-08-27 | 2020-06-26 | 洪昆喨 | High-voltage electro-catalytic discharge reactor |
| CN106247374A (en) * | 2016-09-26 | 2016-12-21 | 天津雾净环保科技有限公司 | A kind of cement revolving tubular kiln low indole coal combustion systems |
| CN110606603A (en) * | 2019-09-30 | 2019-12-24 | 辽宁石油化工大学 | High-efficient pollution-free electrochemistry sewage treatment plant |
| CN110585916B (en) * | 2019-09-30 | 2021-01-12 | 华中师范大学 | Method and device for removing gaseous pollutants through electro-Fenton catalytic oxidation |
| CN111135708B (en) * | 2020-01-13 | 2022-02-08 | 山东中创新材料科技有限公司 | Organic waste gas treatment system and method |
| CN111559791B (en) * | 2020-05-22 | 2023-02-03 | 重庆工商大学 | Spraying type dielectric barrier discharge plasma pollutant treatment device |
| CN116441047B (en) * | 2022-09-05 | 2024-01-16 | 苏州科技大学 | Atomization corona oil smoke waste gas purification device and purification method |
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