CN108325362A - A kind of method that low temperature plasma coupled biological method handles VOCs and foul gas - Google Patents
A kind of method that low temperature plasma coupled biological method handles VOCs and foul gas Download PDFInfo
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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
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/75—Multi-step processes
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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
- B01D53/26—Drying gases or vapours
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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
- B01D53/38—Removing components of undefined structure
- B01D53/44—Organic components
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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
- B01D53/48—Sulfur compounds
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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
- 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
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
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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
- B01D2257/30—Sulfur compounds
- B01D2257/306—Organic sulfur compounds, e.g. mercaptans
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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
- B01D2257/702—Hydrocarbons
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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
- B01D2257/702—Hydrocarbons
- B01D2257/7027—Aromatic hydrocarbons
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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
- 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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Abstract
The present invention relates to the methods of a kind of low temperature plasma coupled biological method processing VOCs and foul gas, include the following steps：(1) it pre-processes；(2) low-temperature plasma degradation；(3) ozone decomposed；(4) biological treatment, wherein step (2) described low-temperature plasma degradation uses low-temperature plasma generator, which includes low-temperature plasma electrical source, is spaced the discharge of plasma in low temperature unit and reaction of low temperature plasma device of laying on gases flow direction.The present invention to VOCs and foul gas by carrying out compartment discharge of plasma in low temperature and biodegradation, it can significantly reduce the compound probability of active particle in low-temperature plasma generator, improve treatment effeciency of the active particle to the degradation efficiency of pollutant in exhaust gas and bio-trickling filter to hardly degraded organic substance.
Description
Technical field
The present invention relates to exhaust-gas treatment fields, specifically, being related to a kind of low temperature plasma coupled biological method processing
The method of VOCs and foul gas.
Background technology
Volatile organic matter (VOCs) is the important sources of atmosphere pollution.A large amount of VOCs are discharged into air, with NOx, SOx,
O3Deng the physical-chemical reaction that complexity occurs, leads to the generation of haze, serious harm is brought to health.Currently, VOCs is normal
The active carbon adsorption of processing method, absorption process, heat-accumulation combustion method, Production by Catalytic Combustion Process, catalytic oxidation, bioanalysis and the light of rule
Catalysis method etc., but many unfavorable factors such as generally existing purification is not thorough, operating cost height.And using plasma technology point
It is a kind of novel method for purifying waste gases to solve all kinds of gaseous pollutant molecules, 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 which using these toxic and harmful gas of Low Temperature Plasma Treating, people are directed to 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
It transmits substantially：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 of the atom and molecule of a large amount of the active particles such as ion, electronics, excitation state that are rich in plasma
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, not high to the utilization rate of active particle.
Patent CN104128083A discloses a kind of side of Biotrickling filter coupled gas barrier discharge degradation foul gas
Method, which preferably solves and generates influence of the ozone to Biotrickling filter after gas barrier discharges, but whole degradation
There is no be fundamentally improved efficiency.
Invention content
The present invention, can by carrying out compartment discharge of plasma in low temperature and bioanalysis degradation to VOCs and foul gas
The compound probability of active particle in low-temperature plasma generator is significantly reduced, active particle in low temperature plasma is improved and degrades
The efficiency of pollutant in exhaust gas improves the efficiency of bio-trickling filter processing hardly degraded organic substance.
To achieve the above object, a kind of low temperature plasma coupled biological method processing VOCs of present invention offer and foul gas
Method, include the following steps：
(1) it pre-processes
VOCs foul gas initially enters total hydrocarbon in-line analyzer and is detected, after testing after gas to enter surge tank slow
After punching, dehumidify into dehumidifier；
(2) low-temperature plasma degradation
Foul gas from dehumidifier enters compartment discharge of plasma in low temperature equipment and degrades；
(3) catalytic decomposition of ozone
Enter catalytic destroyer by the exhaust gas of low-temperature plasma degradation, makes full use of the further pollution degradation of ozone
Object；
(4) biological treatment
Exhaust gas after degradation is sent into biology drop with wind turbine and considers tower, and through bio-trickling filter, treated that exhaust gas is discharged from tower,
Wherein, the exhaust gas inlet line before surge tank is equipped with air distribution pipeline, when exhaust gas concentration be more than compartment low temperature etc. from
Daughter discharge equipment set up defences value when, open air distribution pipeline air inlet；Step (2) the compartment discharge of plasma in low temperature is set
Standby includes low-temperature plasma electrical source, discharge of plasma in low temperature unit and reaction of low temperature plasma device, and two or two
Above discharge of plasma in low temperature unit is inserted into reaction of low temperature plasma device, is spaced and lays in gas flow direction, will
It is divided into region of discharge and non-discharge area between reaction of low temperature plasma device.
Preferably, the time that gas passes through non-discharge area is 0.1s-50s.
Preferably, the spacing distance that discharge of plasma in low temperature unit is laid in gas flow direction can be as needed
It is adjusted.
Preferably, low-temperature plasma electrical source is any one in high voltage power supply, DC power supply, the pulse power, and electric
The output power in source can be adjusted as needed.
Preferably, the discharge type of discharge of plasma in low temperature unit is corona discharge, single gas barrier electric discharge, double gases
Any one in barrier discharge, glow discharge, radio frequency discharge.
Preferably, low-temperature plasma generator is any one in grid type, spool formula or printed line formula.
Preferably, the flow velocity of the plasma discharge VOCs and foul gas is 0.1~17m/s.
Beneficial effects of the present invention：
VOCs and foul gas are handled using compartment low temperature plasma coupled biological method, wherein compartment low temperature etc. from
Daughter uses two or more discharge cells, in the case where total power consumption is certain, compared to other continuous discharge plasmas
The drop filter of body coupled biological, the degradation efficiency of whole device greatly improve.
Description of the drawings
Fig. 1 is the process flow chart that low temperature plasma coupled biological method of the present invention handles VOCs and foul gas；
Fig. 2 is the schematic diagram of compartment discharge of plasma in low temperature equipment of the present invention.
Label declaration：
1- reaction of low temperature plasma devices；2- low-temperature plasma generators；3- low-temperature plasma electrical sources；
4- terminal boxes；5- forms；6- sewage draining exits；7- blow valve ports.
Specific implementation mode
Embodiment 1
As shown in Figure 1, VOCs and foul gas, under the action of centrifugal blower, a part of exhaust gas is by online FID total hydrocarbons point
Analyzer internal pump sucks detector, detects exhaust gas concentration, and the exhaust gas after detection returns to waste line, remaining exhaust gas sequentially enters slow
After rushing the double gas barrier low-temperature plasma generators of tank, dehumidifier, compartment and ozone decomposed instrument, given birth into two-stage series
Object drop filter tower is further degraded, and realizes qualified discharge later.Exhaust gas inlet line before surge tank be equipped with diluent air into
Air port, when exhaust gas concentration be more than compartment discharge of plasma in low temperature equipment set up defences value when, opening diluent air air inlet；It is slow
It is equipped with bypass before rushing tank post plasma equipment, exhaust gas after dilution is more than setting for compartment discharge of plasma in low temperature equipment
When anti-value, exhaust gas is extracted out from bypass.
Dehumidifier operating condition：35 DEG C of summer dehumidifier inlet temperature, outlet exhaust temperature are 30 DEG C, relative humidity 30-
90%；10 DEG C of winter dehumidifier outlet exhaust temperature, outlet exhaust temperature are 20 DEG C, relative humidity 30-90%.
The double gas barrier low-temperature plasma generator setup parameters of compartment are as follows：By 2 single dielectric impedances, spool formulas
Low-temperature plasma generator is spaced laying in gas flow direction, and gas is with each plasma generator time of contact
0.9s, total power input 360W.
The operating condition of the double gas barrier low-temperature plasma generators of compartment is：Exhaust gas is in plasma generation area
By speed be 0.1m/s, be 50s by time of non-discharge area, be 0.9s with plasma generator time of contact,
Discharge voltage is 20kV, and processing tolerance is 200m3/h。
Bio-trickling filter diameter 1.5m, height 1.2m, top has the spray tube of 3 row's uniform pore openings, bottom to be disposed with uniformly
Qi-emitting hole, exhaust gas is up flowed through inside bio-trickling filter by qi-emitting hole and is degraded, when exhaust gas stops in bio-trickling filter
Between be 60s or more.
The organic volatile exhaust gas that certain sewage from oil refinery processing unit generates is taken to be tested, before experiment, benzene contains in exhaust gas
Amount is 80mg/Nm3, after degrading by above-mentioned compartment low-temperature plasma generator, the content of benzene is 24mg/Nm3, benzene removal
For rate up to 70%, the content finally through benzene in bio-trickling filter treated exhaust gas is 3.5mg/Nm3。
Comparative example 1：
According to condition described in embodiment 1 and step, only by the double gas barrier low-temperature plasma generators of compartment
It is changed to General low temperature plasma generator, and setup parameter is as follows：By 1 single dielectric impedance, spool formula low temperature plasma
Generator is laid in gas flow direction, and gas is 1.8s with plasma generator time of contact.
It takes organic exhaust gas same as Example 1 to be tested, degrades by above-mentioned compartment low-temperature plasma generator
Later, the content of benzene is 40.8mg/Nm3, benzene removal rate finally contains through benzene in bio-trickling filter treated exhaust gas up to 49%
Amount is 5.5mg/Nm3。
Embodiment 2
According to condition described in embodiment 1 and step, the difference is that, the setting of compartment low-temperature plasma generator
Parameter is as follows：3 double-dielectric barrier discharge arrays, grating type low-temperature plasma generator interval are laid, total power input
The speed of 360W, gas flowing are 17m/s, and the time by non-discharge area is 0.1s, and gas occurs with each plasma
Device time of contact is 0.1s.
The organic volatile gas exhaust gas that certain sewage from oil refinery processing unit generates is taken to be tested, before experiment, mercaptan in exhaust gas,
The odour concentration content of the foul gas such as thioether is 10000 (dimensionless), is dropped by above-mentioned compartment low-temperature plasma generator
After solution, the odour concentration content of foul gas is 1000 (dimensionless), and removal rate is up to 90%.
Comparative example 2
The setup parameter of General low temperature plasma generator is as follows：By 1 double-dielectric barrier discharge array grating type low temperature
Plasma generator outer electrode is laid in gas flow direction, total power input 360W, and the speed of gas flowing is
1.0m/s, gas are 0.3s with plasma generator time of contact.
Organic exhaust gas same as Example 2 is taken to be tested, it is organic after degrading by low-temperature plasma generator to wave
The odour concentration removal rate of the foul gas such as mercaptan, thioether in exhaust gas of getting angry is only 56%.
Embodiment 3
According to condition described in embodiment 1 and step, the difference is that, the setting of compartment low-temperature plasma generator
Parameter is as follows：2 corona discharges, spool formula low-temperature plasma generator are spaced laying in gas flow direction, it is total defeated
Enter power 360W, the speed of gas flowing is 5m/s, and gas is 0.1s with each plasma generator time of contact, and gas exists
The non-discharge area residence time is 3s.
The organic exhaust gas Volatile Gas that certain sewage from oil refinery processing unit generates is taken to be tested, before experiment, total hydrocarbon in exhaust gas
Content is 760mg/Nm3, after degrading by above-mentioned compartment low-temperature plasma generator, total hydrocarbon content 152mg/Nm3, always
Hydrocarbon removal rate is up to 80%.
Comparative example 3
The setup parameter of General low temperature plasma generator is as follows：1 corona discharge, spool formula low temperature plasma are sent out
Raw device outer electrode is continuously laid in gas flow direction, and total power input 360W, gas is contacted with plasma generator
Time is 0.2s.
Organic exhaust gas same as Example 3 is taken to be tested, the total hydrocarbon after degrading by low-temperature plasma generator
Removal rate is only 60%.
It can be seen that from embodiment 1-3 and comparative example 1-3 and handled using compartment low temperature plasma coupled biological method
VOCs and foul gas, wherein compartment low temperature plasma use two or more discharge cells, certain in total power consumption
In the case of, compared to other continuous discharge plasmon coupling bioanalysis, the former degradation efficiency to VOCs and foul gas
It greatly improves.
Claims (7)
1. the method for a kind of low temperature plasma coupled biological method processing VOCs and foul gas, include the following steps：
(1) it pre-processes
VOCs foul gas initially enters total hydrocarbon in-line analyzer and is detected, after testing after gas enter surge tank buffering
Afterwards, it dehumidifies into dehumidifier；
(2) low-temperature plasma degradation
Foul gas from dehumidifier enters compartment discharge of plasma in low temperature equipment and degrades；
(3) catalytic decomposition of ozone
Enter catalytic destroyer by the exhaust gas of low-temperature plasma degradation, makes full use of the further degradation of contaminant of ozone；
(4) biological treatment
Exhaust gas after degradation is sent into biology drop with wind turbine and considers tower, and through bio-trickling filter, treated that exhaust gas is discharged from tower,
It is characterized in that, the exhaust gas inlet line before surge tank is equipped with air distribution pipeline, when exhaust gas concentration is more than compartment low temperature etc.
Plasma discharge equipment set up defences value when, open air distribution pipeline air inlet；Step (2) the compartment discharge of plasma in low temperature
Equipment includes low-temperature plasma electrical source, discharge of plasma in low temperature unit and reaction of low temperature plasma device, and two or two
A above discharge of plasma in low temperature unit is inserted into reaction of low temperature plasma device, is spaced and lays in gas flow direction,
It will be divided into region of discharge and non-discharge area between reaction of low temperature plasma device.
2. the method for a kind of low temperature plasma coupled biological method processing VOCs according to claim 1 and foul gas,
It is characterized in that, the time that gas passes through non-discharge area is 0.1s-50s.
3. the method for a kind of low temperature plasma coupled biological method processing VOCs according to claim 1 and foul gas,
It is characterized in that, the spacing distance that discharge of plasma in low temperature unit is laid in gas flow direction can carry out as needed
It adjusts.
4. the method for a kind of low temperature plasma coupled biological method processing VOCs according to claim 1 and foul gas,
It is characterized in that, low-temperature plasma electrical source is any one in high voltage power supply, DC power supply, the pulse power, and power supply
Output power can be adjusted as needed.
5. the method for a kind of low temperature plasma coupled biological method processing VOCs according to claim 1 and foul gas,
It is characterized in that, the discharge type of discharge of plasma in low temperature unit is corona discharge, single gas barrier electric discharge, double gas barriers
Any one in electric discharge, glow discharge, radio frequency discharge.
6. the method for a kind of low temperature plasma coupled biological method processing VOCs according to claim 1 and foul gas,
It is characterized in that, low-temperature plasma generator is any one in grid type, spool formula or printed line formula.
7. the method for a kind of low temperature plasma coupled biological method processing VOCs according to claim 1 and foul gas,
It is characterized in that, the flow velocity of the plasma discharge VOCs and foul gas is 0.1~17m/s.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109499350A (en) * | 2018-12-28 | 2019-03-22 | 中科新天地（合肥）环保科技有限公司 | Biodegrade is cooperateed with to administer foul waste gas device and technique based on plasma technique |
| CN110252129A (en) * | 2019-06-19 | 2019-09-20 | 西安交通大学 | A kind of system based on discharge plasma Yu biotechnology Synergistic degradation VOCs |
| CN111185073A (en) * | 2018-11-14 | 2020-05-22 | 中国石油化工股份有限公司 | Method for improving efficiency of low-temperature plasma treatment of VOCs and malodorous gas by regulating humidity |
| CN111420526A (en) * | 2020-03-18 | 2020-07-17 | 郑州轻工业大学 | Application method of low-temperature plasma-biological integrated reaction system |
| CN111715065A (en) * | 2019-03-22 | 2020-09-29 | 中国石油化工股份有限公司 | Volatile organic waste gas degradation reactor, equipment and volatile organic waste gas treatment method |
| CN111871164A (en) * | 2020-06-15 | 2020-11-03 | 浙江工业大学 | Intelligent regulation and control method for low-temperature plasma catalytic degradation of CVOCs |
| CN112782349A (en) * | 2019-11-07 | 2021-05-11 | 中国石油化工股份有限公司 | Organic waste gas detection control method and device |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111185073A (en) * | 2018-11-14 | 2020-05-22 | 中国石油化工股份有限公司 | Method for improving efficiency of low-temperature plasma treatment of VOCs and malodorous gas by regulating humidity |
| CN109499350A (en) * | 2018-12-28 | 2019-03-22 | 中科新天地（合肥）环保科技有限公司 | Biodegrade is cooperateed with to administer foul waste gas device and technique based on plasma technique |
| CN111715065A (en) * | 2019-03-22 | 2020-09-29 | 中国石油化工股份有限公司 | Volatile organic waste gas degradation reactor, equipment and volatile organic waste gas treatment method |
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| CN112782349A (en) * | 2019-11-07 | 2021-05-11 | 中国石油化工股份有限公司 | Organic waste gas detection control method and device |
| CN111420526A (en) * | 2020-03-18 | 2020-07-17 | 郑州轻工业大学 | Application method of low-temperature plasma-biological integrated reaction system |
| CN111871164A (en) * | 2020-06-15 | 2020-11-03 | 浙江工业大学 | Intelligent regulation and control method for low-temperature plasma catalytic degradation of CVOCs |
| CN111871164B (en) * | 2020-06-15 | 2023-03-21 | 浙江工业大学 | Intelligent regulation and control method for low-temperature plasma catalytic degradation of CVOCs |
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Application publication date: 20180727 |
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