CN108339378B - A method of improving Low Temperature Plasma Treating pollutant efficiency - Google Patents
A method of improving Low Temperature Plasma Treating pollutant efficiency Download PDFInfo
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- CN108339378B CN108339378B CN201710409254.2A CN201710409254A CN108339378B CN 108339378 B CN108339378 B CN 108339378B CN 201710409254 A CN201710409254 A CN 201710409254A CN 108339378 B CN108339378 B CN 108339378B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/32—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by electrical effects other than those provided for in group B01D61/00
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/46—Removing components of defined structure
- B01D53/72—Organic compounds not provided for in groups B01D53/48 - B01D53/70, e.g. hydrocarbons
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2251/00—Reactants
- B01D2251/10—Oxidants
- B01D2251/104—Ozone
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/70—Organic compounds not provided for in groups B01D2257/00 - B01D2257/602
- B01D2257/708—Volatile organic compounds V.O.C.'s
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/90—Odorous compounds not provided for in groups B01D2257/00 - B01D2257/708
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2258/00—Sources of waste gases
- B01D2258/02—Other waste gases
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2259/00—Type of treatment
- B01D2259/80—Employing electric, magnetic, electromagnetic or wave energy, or particle radiation
- B01D2259/818—Employing electrical discharges or the generation of a plasma
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- Oil, Petroleum & Natural Gas (AREA)
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- Biomedical Technology (AREA)
- Environmental & Geological Engineering (AREA)
- Treating Waste Gases (AREA)
- Physical Or Chemical Processes And Apparatus (AREA)
Abstract
The present invention relates to a kind of methods for improving Low Temperature Plasma Treating pollutant efficiency, include the following steps: (1) pollutant pre-corrosion；(2) using low-temperature plasma generator to contaminant degradation；(3) pollutant after degrading enters next processing unit, wherein step (2) low-temperature plasma generator uses compartment low-temperature plasma generator, the equipment will be in two or more discharge of plasma in low temperature unit intercalation reaction devices, it is spaced and lays on pollutant flow direction, reaction of low temperature plasma device is partitioned into non-discharge area and region of discharge by low temperature plasma, while ozone-decomposing agent is arranged in non-discharge area.O in plasma generator can be improved in the present invention3The reaction probability of active particle and pollutant reduces secondary pollution and generates probability to further increase the degradation efficiency of pollutant.
Description
Technical field
The present invention relates to pollutant treatment fields, specifically, being related to a kind of raising Low Temperature Plasma Treating pollution
The method of object efficiency.
Background technique
Volatile organic matter (VOCs) is the important sources of atmosphere pollution.A large amount of VOCs are discharged into atmosphere, with NOx, SOx,
O3Deng the physical-chemical reaction that complexity occurs, leads to the generation of haze, bring serious harm to human health.Currently, VOCs is normal
The active carbon adsorption of the processing method of rule, absorption process, heat-accumulation combustion method, Production by Catalytic Combustion Process, catalytic oxidation, bioanalysis and light
Catalysis method etc., but many unfavorable factors such as generally existing purification is not thorough, operating cost height.And using plasma technology point
Solving all kinds of gaseous pollutant molecules is a kind of novel method for purifying waste gases, which, which has, opens the dirt for stopping, handling
Contaminate wide object range, anti-concentration and the advantages that flowed fluctuation ability is strong, purification efficiency is high.
In order to utilize these toxic and harmful gas of Low Temperature Plasma Treating, people are for low-temperature plasma in exhaust-gas treatment
The mechanism of action of body and the method for generating low temperature plasma have carried out a large amount of basic research.Energy in low temperature plasma
Transmitting is substantially are as follows: electronics obtains energy from electric field, converts energy to by colliding the interior energy and kinetic energy of molecule, obtains energy
Molecule be excited, at the same time, moieties are ionized, these particles activated mutually collide so as to cause a series of multiple
Miscellaneous physical-chemical reaction.Because a large amount of active particles for being rich in plasma for example ion, electronics, excitation state atom and molecule
And free radical etc., to provide condition by chemical reaction handling VOCs and odorant for plasma technique.But right
During VOCs and odorant are degraded, when active particle is not often reacted with VOCs and odorant by
The new active particle of newly generated high energy electron excitation is compound, so that the utilization rate of active particle is not high.
Furthermore O can be generated when the discharge medium of low temperature plasma is air or oxygen3, and the service life of ozone is than other
Active particle will be grown, if be not fully utilized, have part O3Molecule by newly generated active particle it is compound fall, do not only result in
The utilization rate of active particle is not high, and can generate secondary pollution, such as nitrogen oxides.
Therefore the compound probability for reducing active particle in low-temperature plasma generator, also means that and improves active grain
The efficiency of son degradation VOCs and odorant, reduce secondary pollution and generate probability.
Although in view of the above-mentioned problems, patent CN204429064U, CN204380489U, CN201830541U,
CN103418217B, CN204485611U, CN203002160U are referred to plural serial stage electric discharge, but the technical side of these patents
Case is the sum of series total power input for simply increasing plasma generator, with the present invention before equal-wattage input
It puts interval and lays plasma generator, the compound probability of active component is effectively reduced, improve the processing to waste water or exhaust gas and imitate
Fruit has essential difference in mechanism and effect；Furthermore the time of every grade of electric discharge is longer in these patents, seeks to put by extending
The electric time improves treatment effect, has essence different from the discharge time for shortening every level-one in this patent.
In addition, O in the active material that low temperature plasma generates3Molecule lasts a long time, if not being fully utilized
Into new plasma generation area, it will by newly generated active particle it is compound fall, do not only result in the utilization of active particle
Rate is not high, and can generate secondary pollution, such as nitrogen oxides.
Summary of the invention
In view of the above-mentioned problems, the present invention passes through among the compartment discharge of plasma in low temperature area along flow direction of medium
Non-discharge area place ozone-decomposing agent, O in low-temperature plasma generator can be improved3Active particle is reacted with pollutant
Probability reduces secondary pollution and generates probability to further increase the degradation efficiency of pollutant.
To achieve the above object, the present invention provides a kind of method for improving Low Temperature Plasma Treating pollutant efficiency, packet
Include following steps:
(1) pollutant first passes through the detection of total hydrocarbon in-line analyzer, dehumidifying, surge tank buffering pretreatment；
(2) it is degraded by pretreated pollutant by low-temperature plasma generator；
(3) pollutant after degradation enters next processing unit,
Wherein step (2) low-temperature plasma generator is compartment low-temperature plasma generator, which includes
Low-temperature plasma electrical source, discharge of plasma in low temperature unit, reaction of low temperature plasma device, two of them or more than two
Discharge of plasma in low temperature unit intercalation reaction device, is spaced on pollutant flow direction and lays, and low temperature plasma is by low temperature
Plasma reactor is partitioned into non-discharge area and region of discharge, places ozone-decomposing agent in non-discharge area.
Preferably, the time for the non-discharge area between discharge cell that pollutant is laid by interval is 0.1s-50s.
Preferably, the ozone-decomposing agent is the carbon-based or molecular sieve for loading Co, Mn, Ni monometallic or bimetallic oxide
Any one in base distintegrant.
Preferably, low-temperature plasma electrical source is high voltage power supply, DC power supply, any one in the pulse power.
Preferably, the electric discharge pattern of discharge of plasma in low temperature unit is corona discharge, single pollutant barrier discharge, double dirts
Contaminate object barrier discharge, glow discharge, any one in radio frequency discharge.
Preferably, low-temperature plasma generator is any one in grid type, spool formula or printed line formula.
Beneficial effects of the present invention are as follows:
(1) present invention is along multiple groups discharge cell is arranged on waste water and exhaust gas flow direction, by between waste water or exhaust gas
Every electric discharge, the compound probability of active particle in low-temperature plasma generator can be reduced, improves active particle to pollutant
Degradation efficiency；
(2) ozone-decomposing agent is placed along the non-discharge area of flow direction of medium, low-temperature plasma generator can be improved
Interior O3The reaction probability of active particle and pollutant further increases the degradation efficiency of pollutant, reduces secondary pollution and generates
Probability.
Below by the variation to organic exhaust gas total hydrocarbon degradation effect, analysis inhibits low temperature plasma active component compound
Effect:
(1) along multiple groups discharge cell is arranged on waste water and exhaust gas flow direction, the disturbance of air-flow can effectively be enhanced,
Promote the mixing of medium, to increase collision and the reaction probabilities of living radical and contaminant molecule, improves living radical
Utilization efficiency.Lab scale, pilot scale and industrial experiment statistics indicate that, open single discharge cell, and dispose behind one not
The discharge cell of unlatching, by two-stage type dielectric barrier discharge equipment compared with not disposing discharge cell thereafter, organic exhaust gas
The degradation efficiency of total hydrocarbon improves 3%；
(2) energy injection of the generation of living radical dependent on discharge process, general feelings during dielectric barrier discharge
Under condition, with the raising of Implantation Energy, the yield of living radical is risen with it, but increase is gradually slack-off, and individually discharges
There are the upper limits for the generation density of the Implantation Energy of unit and living radical.Therefore, it under certain power consumption, is discharged using multiple groups
Unit reasonably distributes energy injection, there is important influence for the yield of living radical.Lab scale and pilot experiment research
Show using single discharge cell, and a discharge cell that do not open is set behind, by putting for two-stage type dielectric impedance
For electric equipment compared with single discharge cell is only arranged, the former total hydrocarbon degradation efficiency is apparently higher than the latter；
(3) experiments have shown that, using two discharge cells, each discharge cell power is 180W, organic exhaust gas and low temperature
Plasma generator time of contact is respectively 0.1s, and the spacing of two low-temperature plasma generators is increased to 1.0m by 0.3m,
Total hydrocarbon degradation efficiency is 81%.In the case where total power consumption is certain, compared to single discharge cell, and increases electric discharge spacing, open
The total hydrocarbon degradation efficiency for opening two groups of discharge cells improves 19%.The reason is that O and O that discharge process generates3Isoreactivity free radical
Density is higher and lasts a long time (> 1s), is generating through first discharge cell and is discharging as the flowing of gas reaches second
It is difficult to completely consume when unit, still has a large amount of O and O on second discharge cell periphery3Isoreactivity free radical, their presence
It can inhibit second discharge cell O and O3Generation, therefore, when two discharge cells arrangement is closer, generated total O and O3
The sum of generated when amount is individually arranged lower than two discharge cells, the adjustable design of spacing is used in the invention, effectively avoids this
One problem.
Detailed description of the invention
Fig. 1 is the position view of ozone-decomposing agent in compartment low-temperature plasma generator of the present invention；
Fig. 2 is the schematic diagram of compartment low-temperature plasma generator of the present invention.
Label declaration:
1- low-temperature plasma generator；2- reaction of low temperature plasma device；3- low-temperature plasma electrical source；
4- terminal box；5- form；6- sewage draining exit；7- blow valve port.
Specific embodiment
Embodiment 1
The setup parameter for filling the compartment low-temperature plasma generator of ozone-decomposing agent layer is as follows: by 2 dielectric impedances
Grating type low-temperature plasma generator is spaced 0.6m laying in the medium flow direction, in two low-temperature plasma generators
Between fill 5cm thickness ozone-decomposing agent layer (the carbon-based distintegrant of load C o), total power input 360W, the speed of media flow
For 0.05m/s, medium and each plasma generator time of contact are 0.9s, and medium is in the non-discharge area residence time
3s。
The organic volatile gas for taking certain sewage from oil refinery processing unit to generate is tested, before experiment, the content of benzene in exhaust gas
For 80mg/Nm3, organic volatile gas first pass through total hydrocarbon in-line analyzer detection, dehumidifying, surge tank buffering pretreatment, subsequently into
After above-mentioned compartment low-temperature plasma generator degradation, the content of benzene is 8mg/Nm3, benzene removal rate is up to 90%.
Comparative example 1
The setup parameter of General low temperature plasma generator is as follows: 2 dielectric impedance grating type low temperature plasmas are sent out
Raw device is spaced 0.6m laying, total power input 360W in the medium flow direction, and the speed of media flow is 0.05m/s, medium
It is 0.9s with each plasma generator time of contact, medium is 3s in the non-discharge area residence time.
Organic volatile gas same as Example 1 is taken to be tested, benzene removal rate is 70%.
Embodiment 2
The setup parameter for filling the compartment low-temperature plasma generator of ozone-decomposing agent layer is as follows: by 2 double medium resistances
Gear, grating type low-temperature plasma generator are spaced 0.6m laying in the medium flow direction, distinguish in the direction of media flow
The ozone-decomposing agent layer (the molecular screen base distintegrant of load Mn) of 5cm thickness is filled after two low-temperature plasma generators,
The distance of low-temperature plasma generator apart from front is 27.5cm, and the speed of total power input 360W, media flow are
0.05m/s, medium and each plasma generator time of contact are 0.9s, and medium is in the residence time of non-discharge area
20s。
The organic volatile exhaust gas for taking certain sewage from oil refinery processing unit to generate is tested, and before experiment, benzene contains in exhaust gas
Amount is 80mg/Nm3, organic volatile gas first pass through total hydrocarbon in-line analyzer detection, dehumidifying, surge tank buffering pretreatment, then into
After entering above-mentioned compartment low-temperature plasma generator degradation, the content of benzene is 4mg/Nm3, benzene removal rate is up to 95%.
Comparative example 2
The setup parameter of General low temperature plasma generator is as follows: by 2 bi-medium to block, grating type low temperature plasma
Generator is spaced 0.6m laying in the medium flow direction, is not provided with ozone-decomposing agent, total power input 360W, media flow
Speed is 0.05m/s, and medium and each plasma generator time of contact are 0.9s, and medium is in the non-discharge area residence time
For 20s.
Organic exhaust gas same as Example 2 is taken to be tested, the removal rate of benzene is 70%.
Embodiment 3
The setup parameter for filling the compartment low-temperature plasma generator of ozone-decomposing agent layer is as follows: by 3 single medium resistances
Gear, spool formula low-temperature plasma generator are spaced 1.0m laying in the medium flow direction, in the direction of media flow often
The ozone-decomposing agent layer (the molecular screen base distintegrant of load Ni) of 5cm thickness, distance are filled after a low-temperature plasma generator
The distance of front low-temperature plasma generator is 47.5cm, total power input 360W, medium and each plasma generator
Time of contact is 0.1s, and medium is 50s in the non-discharge area residence time.
The organic exhaust gas Volatile Gas for taking certain sewage from oil refinery processing unit to generate is tested, before experiment, total hydrocarbon in exhaust gas
Content is 760mg/Nm3, organic volatile gas first pass through total hydrocarbon in-line analyzer detection, dehumidifying, surge tank buffering pretreatment, then
Into after the degradation of above-mentioned compartment low-temperature plasma generator, total hydrocarbon content 80mg/Nm3, total hydrocarbon removal rate is up to 90%.
Comparative example 3
The setup parameter of General low temperature plasma generator is as follows: by 3 single dielectric impedances, spool formula low temperature plasma
Generator outer electrode is spaced 1.0m laying in the medium flow direction, and the speed of total power input 360W, media flow are
0.1m/s, medium and each plasma generator time of contact are 0.1s, and medium is 50s in the non-discharge area residence time.
Organic exhaust gas same as Example 3 is taken to be tested, total hydrocarbon removal rate is 80%.
Embodiment 4
The setup parameter for filling the compartment low-temperature plasma generator of ozone-decomposing agent layer is as follows: by 4 corona discharges
Array, spool formula low-temperature plasma generator interval 1.5m are laid, in the direction of media flow each low temperature plasma
The ozone-decomposing agent layer (the molecular screen base distintegrant of load Mn, Ni bimetallic oxide) of 5cm thickness, distance are filled after generator
The distance of front low-temperature plasma generator is 1.0cm, total power input 360W, and medium connects with each plasma generator
The touching time is 0.1s, and medium is 0.1s in the non-discharge area residence time.
The organic volatile gas exhaust gas for taking certain sewage from oil refinery processing unit to generate is tested, before experiment, mercaptan in exhaust gas,
The odour concentration content of the foul gas such as thioether be 10000, organic volatile gas first pass through total hydrocarbon in-line analyzer detection, dehumidifying,
Surge tank buffering pretreatment, after degrading by above-mentioned compartment low-temperature plasma generator, the evil of foul gas
Smelly levels are 200, and removal rate is up to 98%.
Comparative example 4
The setup parameter of General low temperature plasma generator is as follows: by 4 corona discharge arrays, spool formula low-temperature plasma
Body generator outer electrode is spaced laying, total power input 360W in the medium flow direction, and medium and each plasma are sent out
Raw device time of contact is 0.1s.
Organic exhaust gas same as Example 4 is taken to be tested, the odour concentration removal rate of the foul gas such as mercaptan, thioether
It is 56%.
It can be seen that from above-described embodiment 1-4 and comparative example 1-4 single along arranging that multiple groups are discharged in flow direction of medium
Member by discharging pollutant interval, while placing ozone-decomposing agent along the non-discharge area of flow direction of medium, can be significant
Improve the removal rate of benzene, total hydrocarbon and odor concentration in exhaust gas.
Claims (6)
1. a kind of method for improving Low Temperature Plasma Treating pollutant efficiency, includes the following steps:
(1) pollutant first passes through the detection of total hydrocarbon in-line analyzer, dehumidifying, surge tank buffering pretreatment；
(2) it is degraded by pretreated pollutant by low-temperature plasma generator；
(3) pollutant after degradation enters next processing unit,
It is characterized in that, step (2) low-temperature plasma generator uses compartment low-temperature plasma generator, the equipment
Including low-temperature plasma electrical source, discharge of plasma in low temperature unit, reaction of low temperature plasma device, two of them or two with
On discharge of plasma in low temperature unit intercalation reaction device, on pollutant flow direction be spaced lay, low temperature plasma will
Reaction of low temperature plasma device is partitioned into non-discharge area and region of discharge, places ozone-decomposing agent in non-discharge area.
2. a kind of method for improving Low Temperature Plasma Treating pollutant efficiency according to claim 1, which is characterized in that
The time for the non-discharge area between discharge cell that pollutant is laid by interval is 0.1s-50s.
3. a kind of method for improving Low Temperature Plasma Treating pollutant efficiency according to claim 1, which is characterized in that
The ozone-decomposing agent is appointing in the carbon-based or molecular screen base distintegrant for load Co, Mn, Ni monometallic or bimetallic oxide
It anticipates one kind.
4. a kind of method for improving Low Temperature Plasma Treating pollutant efficiency according to claim 1, which is characterized in that
Low-temperature plasma electrical source is high voltage power supply, DC power supply, any one in the pulse power.
5. a kind of method for improving Low Temperature Plasma Treating pollutant efficiency according to claim 1, which is characterized in that
The electric discharge pattern of discharge of plasma in low temperature unit is corona discharge, single pollutant barrier discharge, double pollutant barrier discharges, brightness
Light electric discharge, any one in radio frequency discharge.
6. a kind of method for improving Low Temperature Plasma Treating pollutant efficiency according to claim 1, which is characterized in that
Low-temperature plasma generator is any one in grid type, spool formula or printed line formula.
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| CN111185049B (en) * | 2018-11-14 | 2022-07-08 | 中国石油化工股份有限公司 | Method for reducing aerosol generated by low-temperature plasma treatment of waste gas through adsorption separation net |
| CN114899087B (en) * | 2022-05-15 | 2023-04-11 | 上海申和投资有限公司 | Wafer plasma cleaning method |
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| US20090324443A1 (en) * | 2006-02-17 | 2009-12-31 | John Christopher Whitehead | Gas treatment |
| US8889079B2 (en) * | 2010-01-13 | 2014-11-18 | Efb, Inc. | Apparatus for removal of particles and VOC from an airstream |
| CN203916426U (en) * | 2014-05-22 | 2014-11-05 | 浙江大学 | A kind of Trinity industrial source peculiar smell emission-control equipment |
| CN204429064U (en) * | 2014-11-28 | 2015-07-01 | 上海译琅环保科技有限公司 | A kind of device of plasma for purification industrial waste gas |
| CN204485611U (en) * | 2015-02-16 | 2015-07-22 | 成都市金臣环保科技有限公司 | A kind of low-temperature plasma industrial |
| CN105066271A (en) * | 2015-08-12 | 2015-11-18 | 无锡伦宝环保科技有限公司 | Multi-ion-field indoor air purifier |
| CN105864908A (en) * | 2016-04-15 | 2016-08-17 | 北京化工大学 | Multistage plasma air purifier |
| CN105833677A (en) * | 2016-04-19 | 2016-08-10 | 中国石油化工股份有限公司 | Method and equipment for treating volatile organic compounds by low-temperature plasma coupling adsorption |
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Effective date of registration: 20221129 Address after: No. 22, Chaoyangmen street, Chaoyang District, Beijing 100020 Patentee after: CHINA PETROLEUM & CHEMICAL Corp. Patentee after: Sinopec Safety Engineering Research Institute Co.,Ltd. Address before: Yanan City, Shandong province Qingdao City three road 266071 No. 218 Patentee before: CHINA PETROLEUM & CHEMICAL Corp. Patentee before: SINOPEC Research Institute OF SAFETY ENGINEERING |