CN1295013C - Method and apparatus for cleaning trace chlorine-arene pollutant in fume - Google Patents
Method and apparatus for cleaning trace chlorine-arene pollutant in fume Download PDFInfo
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- CN1295013C CN1295013C CNB2004100265278A CN200410026527A CN1295013C CN 1295013 C CN1295013 C CN 1295013C CN B2004100265278 A CNB2004100265278 A CN B2004100265278A CN 200410026527 A CN200410026527 A CN 200410026527A CN 1295013 C CN1295013 C CN 1295013C
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- aromatic hydrocarbons
- flue gas
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Abstract
The present invention provides a method and a device for purifying trace quantity of chlorine-arene pollutants in fumes, which is characterized in that fumes containing trace quantity of chlorine-arene toxic organic pollutants are mixed with strong oxidizer loaded with electricity in advance, and then enters a pulse corona discharge plasma area so as to oxidize and decompose the chlorine-arene organic pollutants. The device used for the method for purifying trace quantity of chlorine-arene pollutants in fumes is composed of an atomizer, an electricity loading device, a pulse corona discharge reactor, etc. The present invention overcomes the defect of limitation in the prior art, provides the method and the device which can highly effectively decompose the trace quantity of chlorine-arene organic pollutants in the fumes into innoxious substances, and has the advantages of environmental protection, low energy consumption, convenient installation, etc.
Description
Technical field
The present invention relates to the oxidation Decomposition technology of chlorine aromatic hydrocarbons organic pollution in the industrial waste gas purifying technical field, particularly incinerator smoke.
Background technology
Chlorine aromatic hydrocarbons pollutant mainly contains chlorobenzene, chlorophenol, chlordiphenyl, many chlorodiphenyls to dioxin, polychlorinated dibenzo etc.Chlorine aromatic hydrocarbons pollutant chemistry stability is strong, can continue to exist in environment, is called the continuation organic pollution, in case enter human body by food chain,, can in human body, accumulate because it has high dissolution in fat, cause multiple malignant change after acquiring a certain degree, be detrimental to health.The mainly human various industrial production activities of chlorine aromatic hydrocarbons pollution cause in the ecological environment, and the burning city domestic garbage that especially contains the PVC waste plastics is handled the micro-dioxin contamination thing of discharging, causes environment, health problem.State Environmental Protection Administration has stipulated the emission limit of dioxin in " the consumer waste incineration pollution control criterion " of issue in 2000, require every cubic metre of flue gas must not surpass 1.0 nanogram toxic equivalents to the dioxin of airborne release.
Dioxins in flue gas purifies and adopts active carbon to spray the method (see figure 1) of absorption and deduster combination at present.High-temperature flue gas is after the waste-heat recoverer cooling, remove sour gas at spray column with alkaline absorption solution, again some superperformances activated carbon powder is sprayed continuously and add in the flue gas, dioxin is adsorbed on the activated carbon powder, collect with fiber cloth formula deduster then, the activated carbon powder and the flying dust that will adsorb dioxin are again discharged from deduster together.This method comes down to active carbon is transferred in dioxins in flue gas absorption, dioxin does not obtain degraded, the powdered carbon and the fly ash mixture of discharging from deduster generally contain dioxin 1 to 20ng-TE/g, these solid slags must carry out landfill disposal as danger, and wherein dioxin also can cause landfill sepage water to pollute in the long run.The bulky refuse incineration plant is used charcoal absorption technical finesse dioxin usually now, exists the operating cost height, needs to handle shortcomings such as containing the dioxin waste residue.
The dioxin catalytic degradation technology in addition that recent research is more, recent research is more also has dioxin catalytic degradation technology, for example WO0067880 disclose a kind of utilize that titanium dioxide and tungsten thereof, vanadium additive prepare, at the catalyst that also has the dioxin degrading activity below 250 ℃; EP0914877 utilizes the dechlorination of amine or ammonium compounds, is decomposing the dioxin contamination thing below 300 ℃; JP2001029786 discloses dioxin degradation catalyst and the technique for applying that utilizes titanium dioxide, vanadium oxide and the preparation of manganese compounds thereof.The advantage of catalytic degradation technology is that dioxin is decomposed into innocuous substance, avoids secondary pollution.Its limitation is: (1) dioxins in flue gas content is generally ng/Nm
3The order of magnitude, this situation require catalyst to have very high selectivity.(2) owing to technical process, effects of operation conditions, flue-gas temperature changes greatly, and catalyst will have suitable activity in wide temperature range.(3) the incineration plant flue gas often contains composition and compounds thereof such as lead, mercury, sulphur, easily causes catalyst poisoning, requires catalyst that good resistance toxicity energy is arranged.
Summary of the invention
The objective of the invention is to overcome the limitation of prior art, a kind of method that can expeditiously micro-chlorine aromatic hydrocarbons organic pollution in the flue gas be resolved into innocuous substance is provided.
The main component of incineration plant flue gas is N
2, CO
2, H
2O, O
2Deng, chlorine aromatic hydrocarbons toxic organic pollutant is extremely micro-, is low to moderate ng/Nm
3Therefore the order of magnitude, is difficult to handle with methods such as conventional absorption, absorption, catalytic oxidations.Chlorine aromatic hydrocarbons molecular difference is in flue gas main component N
2, CO
2, H
2O, O
2One of characteristics of molecule are its electron affinity (electron affinity), N
2Molecule has very weak electron affinity, CO
2, H
2O, O
2Molecule has weak electron affinity, and chlorine aromatic hydrocarbons molecule has very strong electron affinity.Utilize this characteristics, with the strong oxidizer of pre-bear electricity for example hydrogen peroxide mix with flue gas, can be so that the hydrogen peroxide of bear electricity optionally combines with chlorine aromatic hydrocarbons molecule.In addition, utilize corona discharge pulse to produce non-equilibrium plasma, chemical reaction in the nonequilibrium plasma mainly is to finish by the fast electron excitation that gas discharge produces, these fast electronics and gas molecule collisions, make gas molecule be energized into more high level, be excited to high level molecule since in it can increase, the fracture that key both can take place also can with other species generation chemical reaction, and collision loses the electronics of portion of energy and still can be compensated under electric field action.Therefore, the electronics with high activity, atom, molecule and free radical and organic pollutant molecule reaction that the nonequilibrium plasma technology utilizes gas discharge to produce, thus make contaminant molecule be decomposed into micromolecular compound.When the flue gas that contains micro-chlorine aromatic hydrocarbons toxic organic pollutant when entering the corona discharge pulse plasma slab after the strong oxidizer hydrogen peroxide of pre-bear electricity mixes, plasma can activate organic pollutant molecule generation deep oxidation and degrade, and finally is oxidized to CO
2And H
2O.
Based on above principle, the present invention proposes a kind of micro-chlorine aromatic hydrocarbons organic pollution in the flue gas to be resolved into the method for innocuous substance, is made of following steps:
(1) with the pre-bear of strong oxidizer hydrogen peroxide;
(2) the strong oxidizer hydrogen peroxide with pre-bear electricity mixes with flue gas;
(3) mixed flue gas enters the corona discharge pulse reactor, chlorine aromatic hydrocarbons organic pollution oxidation Decomposition.
The application flow of this method is shown in Fig. 2.
State in realization in the device of method, extract little air with blower fan and feed the interior ultrasonic ultrasonic delay line memory of containing hydrogenperoxide steam generator, ultrasonic ultrasonic delay line memory is fine droplet with the hydrogenperoxide steam generator atomizing, and these atomizing hydrogen peroxide are brought to charge electric appliance by air.High pressure negative electrode and earthing pole are arranged in the charge electric appliance, form faint discharge stream between high pressure negative electrode and the earthing pole, the hydrogen peroxide bear is crossed between high pressure negative electrode and the earthing pole in the circulation of air of atomizing hydrogen peroxide, directly spray into flue gas by the charge electric appliance outlet then, fully mix with flue gas.Mixed flue gas enters the corona discharge pulse reactor again, the corona discharge pulse reactor is made of discharge electrode and earthing pole, discharge electrode connects pulsed high voltage generator, form the pulsed discharge non-equilibrium plasma between discharge electrode and the earthing pole, mixed flue gas is by plasma slab, the oxidized decomposition of micro-chlorine aromatic hydrocarbons toxic organic pollutant wherein.
The micro-chlorine aromatic hydrocarbons pollutant that uses this method to purify in the flue gas has the following advantages:
(1) do not produce waste liquid, the waste residue that contains poisonous organic pollution;
(2) adopt the corona discharge pulse plasma, belong to non-mode of heating, energy consumption is lower;
(3) apparatus structure is simple, volume is little, can utilize existing flue to install;
(4) the flow of flue gas resistance is less in the device.
Description of drawings
Below in conjunction with accompanying drawing flesh and blood of the present invention is further described:
Fig. 1 is the prior art processes flow process;
Fig. 2 is technological process of the present invention;
Fig. 3 is the schematic diagram of apparatus of the present invention;
Fig. 4 is the schematic diagram of oxidant injection mode;
Fig. 5 is the charge electric appliance structural representation;
Fig. 6 is the vertical view of charge electric appliance;
Fig. 7 is a corona discharge pulse reactor discharge electrode schematic diagram;
Fig. 8 is a corona discharge pulse reactor earthing pole schematic diagram.
The specific embodiment
A kind of purifier that is used for the micro-chlorine aromatic hydrocarbons of flue gas pollutant of design as shown in Figure 3 according to the present invention.In processing procedure, feed ultrasonic ultrasonic delay line memory 2 with blower fan 3 extracting airs, contain hydrogenperoxide steam generator (the about 35wt%H of concentration in the ultrasonic ultrasonic delay line memory
2O
2The aqueous solution), hydrogen peroxide is atomized to bringing to charge electric appliance 1 by air behind the fine droplet, directly sprays into flue gas by the charge electric appliance outlet behind the hydrogen peroxide bear electricity, fully mixes with flue gas.Mixed flue gas enters the corona discharge pulse reactor part that is made of discharge electrode 4 and earthing pole 7 again, and discharge electrode 4 is by pulsed high voltage generator 6 power supply, and insulator 5 makes discharge electrode and flue wall isolated.Charge electric appliance 1 is about 500mm with the spacing of the corona discharge pulse utmost point 4, and the corona discharge pulse utmost point 4 is about 200-300mm with the spacing of earthing pole 7.Pulsed high voltage generator adopts prior art, and major parameter is as follows: crest value of impulse voltage is higher than 50kV (being preferably 60-70kV), the about 5 μ s of pulse width, rising edge of a pulse in 200ns, the about 500ns of trailing edge, the about 50-100Hz of pulse frequency.
Fig. 4 represents the spray regime of hydrogen peroxide oxidant.Be positioned at wall center line one side at the flue wall, every wall is arranged two charge electric appliances 1, makes to form bumpy flow when hydrogen peroxide oxidant sprays into flue, fully mixes with flue gas.Use a typhoon machine 3 to provide air to all charge electric appliances, available adjustment valve 4 is regulated the air capacity of the ultrasonic ultrasonic delay line memory 2 that enters each charge electric appliance separately.
Fig. 5 is the charge electric appliance structural representation.Charge electric appliance outer wall 4 usefulness internal diameter 40mm steel pipe manufacturings, and link to each other with ground wire, earthing pole become.Have external diameter to be about the steel pipe 1 of 8mm in the charge electric appliance, the steel pipe bottom is installed in the charge electric appliance bottom wall, and insulator 5 makes that steel pipe 1 and charge electric appliance outside wall surface are isolated.Have the aperture that a series of directions are alternately arranged on the steel pipe 1, draw point 2 and 3 modes with immovable fitting are installed in these apertures (as shown in Figure 5 and Figure 6).Draw point 2 and the about 1mm of 3 diameters are about 16mm, and have sharp-pointed tip.The output of 5-10kV DC high-voltage power supply 6 links to each other with 3 with steel pipe 1, draw point 2, steel pipe 1, draw point 2 and 3 become the high pressure negative electrode, produce the direct current ebb-flow discharge between draw point 2 and 3 tip and the earthing pole 4, these direct current ebb-flow discharge zones are crossed in the circulation of air of atomizing hydrogen peroxide, make the hydrogen peroxide bear, spray into flue gas from the charge electric appliance outlet then, mix with flue gas.The preferred configuration of the output voltage of DC high-voltage power supply 6 is between 5 to 10kV.
Figure 7 shows that corona discharge pulse reactor discharge electrode, the corona wire 1 that the about 1.5mm steel wire of several diameters is made, space 100mm vertically is installed in the flue, and the insulator 2 assurance corona discharge pulse utmost points and flue wall are isolated, and corona wire 1 is connected with pulsed high voltage generator 3 outputs.
Figure 8 shows that corona discharge pulse reactor earthing pole, make, vertically be installed in the flue, and link to each other with ground wire of the steel wire of the about 20 * 20mm of pitch-row.
Above-mentioned chlorine aromatic hydrocarbons pollutant purification device can be applicable to the garbage burning factory flue gas and handles, and its technological process is shown in Fig. 2.High-temperature flue gas is after the waste-heat recoverer cooling; remove sour gas and part lime-ash at spray column with alkaline absorption solution; remove fine dusts with fiber cloth formula deduster then; the flue gas of discharging from fiber cloth formula deduster enters the corona discharge pulse reactor again; under the acting in conjunction of strong oxidizer hydrogen peroxide and impulse electric corona plasma; chlorine aromatic hydrocarbons organic pollution is decomposed by complete oxidation, and the fume emission after the processing can reach State Environmental Protection Administration's " consumer waste incineration pollution control criterion ".
Claims (5)
1, a kind of method that purifies micro-chlorine aromatic hydrocarbons pollutant in the flue gas is characterized in that entering the corona discharge pulse plasma slab with oxidation Decomposition chlorine aromatic hydrocarbons organic pollution with after containing the flue gas of micro-chlorine aromatic hydrocarbons toxic organic pollutant and the strong oxidizer of bear electricity mixing in advance.
2, the method for micro-chlorine aromatic hydrocarbons pollutant in the described purification flue gas of claim 1 is characterized in that may further comprise the steps:
(1) strong oxidizer with pre-bear electricity mixes with flue gas;
(2) mixed flue gas enters the corona discharge pulse reactor.
3, the method for micro-chlorine aromatic hydrocarbons pollutant in claim 1 or the 2 described purification flue gases is characterized in that employed strong oxidizer is a hydrogen peroxide.
4, the method for micro-chlorine aromatic hydrocarbons pollutant in claim 1 or the 2 described purification flue gases, the output voltage of charge electric appliance DC high-voltage power supply is 5 to 10kV when it is characterized in that pre-bear electricity.
5, the method for micro-chlorine aromatic hydrocarbons pollutant in claim 1 or the 2 described purification flue gases, the crest value of impulse voltage that it is characterized in that the corona discharge pulse reactor is 60-70kV.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100265278A CN1295013C (en) | 2004-03-18 | 2004-03-18 | Method and apparatus for cleaning trace chlorine-arene pollutant in fume |
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|---|---|---|---|
| CNB2004100265278A CN1295013C (en) | 2004-03-18 | 2004-03-18 | Method and apparatus for cleaning trace chlorine-arene pollutant in fume |
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|---|---|
| CN1669623A CN1669623A (en) | 2005-09-21 |
| CN1295013C true CN1295013C (en) | 2007-01-17 |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AU2010279703A1 (en) * | 2009-08-03 | 2012-02-23 | Fmc Corporation | Activation of reactive compound with catalyst |
| CN103357255B (en) * | 2012-04-10 | 2015-05-13 | 杭州中兵环保股份有限公司 | Device and method for organic waste gas by oxidizing and cracking |
| CN105854568B (en) * | 2016-06-07 | 2018-05-04 | 南京蓝色天空环保科技有限公司 | Low-temperature denitration flue reative cell |
| CN112973407B (en) * | 2021-02-03 | 2022-06-14 | 浙江天蓝环保技术股份有限公司 | Deodorization system and process for efficient absorption of waste gas and synergistic free radical oxidation |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20010055809A (en) * | 1999-12-13 | 2001-07-04 | 이구택 | Additional Ceramic Roll for Reducing Drosses in CGL Line |
| CN1328865A (en) * | 2000-06-02 | 2002-01-02 | 黄立维 | Method for removing harmful gas containing fluorine, chlorine, sulfur or nitrogen from gas flow |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20010055809A (en) * | 1999-12-13 | 2001-07-04 | 이구택 | Additional Ceramic Roll for Reducing Drosses in CGL Line |
| CN1328865A (en) * | 2000-06-02 | 2002-01-02 | 黄立维 | Method for removing harmful gas containing fluorine, chlorine, sulfur or nitrogen from gas flow |
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Granted publication date: 20070117 Termination date: 20140318 |