CN100540121C - A method and device for treating industrial waste gas with dual plasma - Google Patents

A method and device for treating industrial waste gas with dual plasma Download PDF

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CN100540121C
CN100540121C CNB2006100280188A CN200610028018A CN100540121C CN 100540121 C CN100540121 C CN 100540121C CN B2006100280188 A CNB2006100280188 A CN B2006100280188A CN 200610028018 A CN200610028018 A CN 200610028018A CN 100540121 C CN100540121 C CN 100540121C
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waste gas
gas
area
pressure gas
discharge
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CN1915479A (en
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张仁熙
侯惠奇
苏小红
顾丁红
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Fudan University
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Abstract

本发明属废气处理技术领域，具体为一种双等离子体处理工业废气的方法与装置。该方法由一台等离子体电源同时实现二个区域的介质阻挡放电：常压气体放电区(简称I区)和低压气体紫外辐射区(简称II区)，待处理废气由I区进入系统，再经过II区紫外辐射，提高了污染物的去除效率。装置由3个直径不同的石英管和内外电极组成，三个石英管之间形成上述2个放电区。本发明的双等离子体反应系统同常压气体介质阻挡放电系统相比，外施电压降低3000V左右，能量利用率提高30%；该系统结构紧凑，能效高，处理效果好，可用于多种工业废气的除污处理。

The invention belongs to the technical field of waste gas treatment, in particular to a method and device for treating industrial waste gas with dual plasma. In this method, a plasma power supply realizes the dielectric barrier discharge in two areas at the same time: the normal pressure gas discharge area (abbreviated as I area) and the low pressure gas ultraviolet radiation area (abbreviated as II area), and the waste gas to be treated enters the system from I area, and then After the ultraviolet radiation in zone II, the removal efficiency of pollutants is improved. The device consists of three quartz tubes with different diameters and internal and external electrodes, and the above two discharge areas are formed between the three quartz tubes. Compared with the normal pressure gas dielectric barrier discharge system, the double plasma reaction system of the present invention reduces the applied voltage by about 3000V and increases the energy utilization rate by 30%; the system has compact structure, high energy efficiency and good treatment effect, and can be used in various industries Waste gas decontamination treatment.

Description

A kind of method and apparatus for the treatment of industrial waste gas through dual plasma
Technical field
The invention belongs to technical field of waste gas treatment, be specifically related to a kind of method and apparatus of plasma industrial waste gas treatment.
Background technology
In the industrial waste gas processing method, lower temperature plasma technology is compared with other pollution control technology, has characteristics such as handling process is short, floor space is little, vapour lock is little, applied widely.The principle that lower temperature plasma technology is handled pollutant is: under the effect of extra electric field, the energy electronics is taken in the gas discharge generation in a large number, and (the electronics average energy is 1～10eV), ionization takes place, dissociates or excites in the odorant in the waste gas under the bombardment of high energy electron, and at O 2Participate in a series of complexity take place down in reaction physics, chemical reaction, finally make the pollutant decomposition in the waste gas reach the purification purpose.
Plasma is the 4th attitude that is called as material after solid-state, liquid, gaseous state, it be gas in discharge process, produce comprise a kind of quasi-neutrality gas that shows collective behavior that a large amount of positive and negative charged particles, electronics and neutral particle and free radical are formed.If the temperature difference of the temperature of electronics and heavy particle is few in this individual system, is high-temperature plasma then, or is called the equilibrium state plasma.If the temperature of electronics is far longer than the temperature of heavy particle, whole system presents a kind of normal temperature state, and the plasma that produce this moment is a low temperature plasma, also is non-equilibrium plasma, and the plasma that general gas discharge produces belongs to this type.Mode according to gas discharge, the generation of plasma mainly contains glow discharge (Glowdischarge), corona discharge (Corona discharge), dielectric barrier discharge (Dielectric barrier discharge is called for short DBD), radio frequency discharge (Radio frequency discharge) and microwave discharge (Microwave discharge) etc.Wherein dielectric barrier discharge has the advantages that electron density is high and can move under normal pressure, thereby makes it have prospects for commercial application, is specially adapted to the improvement of industrial waste gas.See the early stage patent of applicant: dielectric barrier discharge produces the plasma industrial waste gas treatment method and apparatus (patent No.: ZL97242751.1).
Although it is obvious that dielectric barrier discharge plasma is handled industrial waste gas (comprising foul gas) effect, technology is succinct, advantage is remarkable, but in order to reach the treatment effect of expection, therefore often need higher applied voltage (generally being greater than 9000V), to the having relatively high expectations of electric equipment, equipment investment is big, energy consumption is also higher, thereby its popularization and use are restricted.
Summary of the invention
The objective of the invention is to propose the method and apparatus that a kind of equipment requirement is low, energy consumes little plasma industrial waste gas treatment.
The method of the plasma industrial waste gas treatment that the present invention proposes, it is the improvement of existing dielectric barrier discharge plasma being handled the industrial waste gas method, change three layers of quartz medium layer into by original double-deck quartz medium, three floor quartz medium are cut apart formed two region of discharges: atmosphere gas region of discharge and low pressure gaseous discharge district, the low pressure gaseous discharge nip produces ultra-violet radiation; Industrial waste gas enters system by the atmosphere gas region of discharge, through the low-pressure gas ultraviolet radiation zone, realizes the efficient effect of removing pollutant, Purge gas.Like this, make reactor under the situation that is equipped with a power supply, realize two kinds of process gas discharges, promptly under normal pressure, the process gas discharge, realize that also low pressure gaseous discharge produces the ultra-violet radiation process.Because this system has increased plasma ultra-violet radiation process under the low pressure than simple dielectric barrier discharge plasma technique, so be referred to as the method that " double plasma " handles industrial waste gas.
Low pressure gaseous discharge ultra-violet radiation principle is: fill low-pressure gas and be generally rare gas and halogenic molecule in the airtight toroidal cavity of ultraviolet radiation zone, in the dielectric barrier discharge process these gas molecules be excited, ionization, and through series reaction formation quasi-molecule, the quasi-molecule instability produces ultra-violet radiation in its decomposition or de excitation process.Main course of reaction is as follows:
1. ionization and exciting
At first be that the low-pressure gas molecule is excited and ionization under the effect of high energy electron:
R+e→R *+e
R+e→R ++2e
X 2+e→X+X -
R represents that (as aR, Kr), X represents halogen particle (as Cl, Br or I) to the rare gas particle.
2. the generation of quasi-molecule
Electropositive noble gas ion and electronegative halide ion rare gas particle compound or excitation state passes to halogenic molecule to energy and forms the RgX of excitation state *The quasi-molecule compound:
R ++X -→RX *+e
R *+X 2→RX *+X
3. radiation
Quasi-molecule of Xing Chenging or quasi-molecule compound instability are understood rapidly and are decomposed like this, and discharge excitation energy with the form of photon:
RX *→R+X+hυ
Suitably the pressure and the composition of control low-pressure gas can obtain our needed ultra-violet radiation type low-pressure gas.The photon energy that ultraviolet radiation zone produces generally is controlled between 4～8eV, and contaminant molecule issues biochemical bond fission in the effect of these photons, and causes a series of oxidation reactions, thereby reaches the purpose of waste gas purification.In the double plasma reactor, owing to have gas discharge and ultra-violet radiation synergy decomposing pollutant, thereby improved the clearance of pollutant.
The present invention corresponding to the apparatus structure of the treating industrial waste gas through dual plasma of said method as shown in Figure 1.This device is that the double plasma reactor is made up of outer media 1, intermediate layer medium 2, internal layer medium 3, external electrode 4, interior electrode 5, high voltage source and support member 8; Wherein, outer media 1, intermediate layer medium 2 and internal layer medium 3 adopt the different quartz ampoule of diameter respectively, make 2 in outer media 1 and intermediate layer medium form the atmosphere gas region of discharge, form the low-pressure gas ultraviolet radiation zone between middle dielectric layer 2 and the internal layer medium 3; Interior electrode 5 places internal layer medium 3, and external electrode 4 is wound in outer media 1 outside; Support member 8 is supported between outer media 1 and the intermediate layer medium 2.Pending industrial waste gas enters reaction system by the atmosphere gas region of discharge.
This double plasma reaction system is compared with simple dielectric barrier discharge plasma, and capacity usage ratio improves 30%, and applied voltage reduces (as long as generally 6000-7000) about 3000V, and the pipeline gas flow velocity is generally 2-4m/s.Under the identical situation of input energy, the removal efficient of odorant improves more than 30%.
Treating industrial waste gas through dual plasma, the pollutant treatment effect is good, and the efficiency height can be widely used in containing the waste gas pollution control and treatment of materials such as triphen (benzene,toluene,xylene), hydrogen sulfide, carbon disulfide, and its promotion and application have a extensive future.
Description of drawings
Fig. 1 is a double plasma structure of reactor diagram of the present invention.
Fig. 2 is the cross-sectional diagram of Fig. 1 reactor.
Fig. 3 is the vertical profile diagram of Fig. 1 reactor.
Fig. 4 is the supporting piece structure diagram.
Fig. 5 is the workflow diagram.
Number in the figure: 1 is outer media, and 2 is the intermediate layer medium, and 3 is the internal layer medium, and 4 is external electrode, and 5 is interior electrode, and 6 is the atmosphere gas region of discharge, and 7 is the low-pressure gas ultraviolet radiation zone, and 8 is support member, and 9 is feet, and 10 is hollow ring.
The specific embodiment
Further describe the present invention below by embodiment and accompanying drawing.
Outer media 1 adopts the quartz ampoule of internal diameter 33mm, wall thickness 1.5mm, pipe range 200mm.Intermediate layer medium 2 adopts the quartz ampoule of internal diameter 20mm, pipe range 200mm, wall thickness 1.5mm; Internal layer medium 3 adopts the quartz ampoule of external diameter 10mm, pipe range 200mm, wall thickness 1.0mm.
(thickness δ=0.4mm), be wound in outer quartzy tube wall (6 circle) and form, the distance between circle and the circle is 4mm to the elongated stainless steel substrates of external electrode 4 employing length * wide=670mm * 4mm.(thickness δ=0.2mm) rolls and forms interior electrode 5 usefulness length * wide=200mm * 40mm stainless steel substrates, and liner is at the inner tubal wall of internal layer quartz ampoule 3.
As shown in Figure 2, the zone between the quartz ampoule in skin and intermediate layer is atmosphere gas region of discharge 6 (being called for short the I district), and this district is long 200mm, the open toroidal cavity of ring width 5mm, and pending industrial waste gas promptly passes through from this.The quartz ampoule two ends in internal layer and intermediate layer bond together respectively, form a long 200mm, fill low-pressure gas in the airtight toroidal cavity of ring width 5mm, cavity, and this toroidal cavity is the zone 7 (being called for short the II district) that produces the low-pressure gas ultra-violet radiation.
Support member 8 between the quartz ampoule in outer quartz ampoule and intermediate layer is a triangular ring, is enclosed within the outer tube wall of intermediate layer quartz ampoule, and material is a poly fourfluoroplastics.Supporting piece structure as shown in Figure 4.Hollow ring 10 internal diameter 23mm, external diameter 26mm, three leg 9 length * wide=3.5mm * 2mm, annulus and leg thickness are 3mm.
The high voltage source self-control, output voltage 1500～12000V.
The pressure of blanketing gas is the important parameter that influences the ultra-violet radiation performance, to the ultra-violet radiation Energy distribution, and output characteristics, the shape and the relative intensity of ultra-violet radiation spectrum have considerable influence.According to the composition difference in the waste gas, in airtight annular housing, fill the low-pressure gas of suitable pressure and component, it is given off the most effective ultraviolet light of specific wavelength of the decomposition of pollutant in the waste gas, and the electronics synergy that produces with dielectric barrier discharge, thereby reach best pollutants removal rate.
The present invention is directed to carbon disulfide, hydrogen sulfide, three benzene gas (benzene,toluene,xylene), dimethyl disulfide, ammonia and five kinds of materials of styrene respectively as handling object, determine that the blanketing gas component and the pressure that are adopted are shown in Table 1.
Pairing ultra-violet radiation type of the different odorants of table 1 and correlated condition
Odorant Institute's blanketing gas component in the interior dielectric-sleeve Institute's blanketing gas pressure in the interior dielectric-sleeve Ultraviolet radiation wave-lengths The dielectric barrier discharge applied voltage
Carbon disulfide CS 2 Krypton and iodine vapor Krypton: 200～350torr iodine vapor: 2～3.5torr Mainly: 183nm is a small amount of: 191,206, and 342nm 6000～7500V
Hydrogen sulfide H 2S Krypton and bromine vapor Krypton: 1～10torr bromine vapor: 0.5～1torr Mainly: 207nm is a small amount of: 222, and 228nm 6000～7500V
Benzene,toluene,xylene Argon and bromine vapor Krypton: 1～5torr bromine vapor: 0.5～1torr Mainly: 165,172,183nm 6000～7500V
Ammonia NH 3 Argon and chlorine Argon: 200～300torr chlorine: 0.5～1torr Mainly: 175nm is a small amount of: 195, and 245nm 5000～6000V
Styrene C 6H 5CH＝CH 2 Krypton and iodine Krypton: 200～300torr iodine: 3～4torr Mainly: 206,183,187nm is a small amount of: 253.7nm 5000～6000V
Dimethyl disulfide CH 3SSCH 3 Krypton and chlorine Krypton: 200～300torr chlorine: 0.8～2torr Mainly: 222nm is a small amount of: 240,200, and 325nm 6000～7500V
(annotate: 1torr=133.33Pa)
The carbon disulfide of selecting one of country's " odorant pollutant discharge standard " representative odorant in (GB14554-93) for use illustrates the treatment effect of double plasma technology as handling object.
The technical process of implementing as shown in Figure 5.
Flowmeter: spinner flowmeter, flow＜100m 3/ h is adjustable.
The double plasma reactor: 10, the specifications parameter face that sees before is described, disposal ability 50m 3/ h.
Air-introduced machine: CZR type centrifugal induced draught fan, last Haixing County benefit blower fan factory, power 40W, air quantity 1.07m 3/ min.
The sampling of carbon disulfide and assay method adopt standard GB/T 14680-93 diethylamine spectrophotometry.
Under the effect of air-introduced machine, concentration is 105mg/m 3CS 2Foul gas quantitatively enters the double plasma reaction unit, behind the high energy electron and ultra-violet radiation effect through the generation of double plasma reactor, in the outlet 1m of reactor place's sampling analysis, for the accuracy that guarantees to sample, the fixed-site of each sampling, and sampling again behind reactor stable operation 30min.
For investigating the effect for the treatment of industrial waste gas through dual plasma, the present invention is in implementation process, adopt simple dielectric barrier discharge plasma device to oppose than test, simple dielectric barrier discharge plasma reactor is except that the quartz medium layer, and the member of reactor and specification are all identical with the double plasma reactor.In simple dielectric barrier discharge reactor, outer quartz medium is the quartz ampoule of internal diameter 33mm, wall thickness 1.5mm, pipe range 200mm; The internal layer quartz medium is the quartz ampoule of internal diameter 20mm, wall thickness 1.5mm, pipe range 200mm.
Treatment effect:
Gas flow rate is 3m/s in pipeline, CS 2Concentration 105mg/m 3, to fill under the condition of 350torr krypton and 3.5torr iodine vapor in the applied voltage 6000V, airtight toroidal cavity, the clearance of carbon disulfide is 73%, has improved 30% than simple dielectric barrier discharge plasma.
Except execute outside the voltage, under the constant situation of other condition, double plasma reactor and simple dielectric barrier discharge plasma reactor reach 70% CS respectively 2During clearance, the latter's applied voltage need reach 9000V, and the former only needs 6000V to get final product, and has reduced 3000V, and therefore, the double plasma reactor is higher than simple dielectric barrier discharge plasma efficiency.

Claims (4)

1、一种双等离子体处理工业废气的方法，其特征在于由原来的双层石英介质改为三层石英介质层，使三层石英介质分割形成两个放电区域：常压气体放电区和低压气体紫外辐射区；工业废气由常压气体放电区进入系统，经过低压气体紫外辐射区，实现去除污染物、净化气体的效果。1. A method for treating industrial waste gas with double plasma, which is characterized in that the original double-layer quartz medium is changed to three-layer quartz medium layer, so that the three-layer quartz medium is divided to form two discharge areas: a normal-pressure gas discharge area and a low-pressure gas discharge area. Gas ultraviolet radiation area; industrial waste gas enters the system from the normal pressure gas discharge area, and passes through the low pressure gas ultraviolet radiation area to achieve the effect of removing pollutants and purifying the gas. 2、根据权利要求1所述的方法，其特征在于低压气体紫外辐射区的光子能量控制在4-8eV之间。2. The method according to claim 1, characterized in that the photon energy in the low-pressure gas ultraviolet radiation region is controlled between 4-8eV. 3、根据权利要求1所述的方法，其特征在于外施电压为6000-7000V，管道气体流速度2-4m/s。3. The method according to claim 1, characterized in that the applied voltage is 6000-7000V, and the pipeline gas flow velocity is 2-4m/s. 4、根据权利要求1所述的方法，其特征在于低压气体紫外辐射区的空腔内填充的低压气体的组分和压强分别为：4. The method according to claim 1, characterized in that the composition and pressure of the low-pressure gas filled in the cavity of the low-pressure gas ultraviolet radiation area are respectively: ①.200～350torr氪和2～3.5torr的碘蒸气，主要处理含二硫化碳的废气；①.200~350torr krypton and 2~3.5torr iodine vapor, mainly for the treatment of waste gas containing carbon disulfide; ②.1～10torr氪和0.5～1torr的溴蒸气，主要处理含硫化氢的废气；②. 1-10 torr krypton and 0.5-1 torr bromine vapor, mainly to treat waste gas containing hydrogen sulfide; ③.1～5torr氩和0.5～1torr的溴蒸气，主要处理含苯、甲苯和二甲苯的废气；③. 1-5torr argon and 0.5-1torr bromine vapor, mainly to treat waste gas containing benzene, toluene and xylene; ④.200～300torr氩和0.5～1torr的氯，主要处理含氨的废气；④. 200-300 torr argon and 0.5-1 torr chlorine, mainly for treating waste gas containing ammonia; ⑤.200～300torr氪和3～4torr的碘蒸气，主要处理含苯乙烯的恶臭气体；⑤. 200~300torr krypton and 3~4torr iodine vapor, mainly dealing with malodorous gas containing styrene; ⑥200～300torr氪和0.8～2torr的氯，主要处理含二甲二硫醚的恶臭气体。⑥Krypton of 200～300torr and chlorine of 0.8～2torr, mainly deal with the malodorous gas containing dimethyl disulfide.
CNB2006100280188A 2006-06-22 2006-06-22 A method and device for treating industrial waste gas with dual plasma Expired - Fee Related CN100540121C (en)

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CN101391171B (en) * 2008-10-23 2011-05-04 上海大学 Low-temperature plasma purifier
CN104014233B (en) * 2012-12-26 2015-12-02 江苏理工学院 The device of Excimer UV radiation degrade waste gas integrated with plasmon coupling
CN104474886B (en) * 2013-03-20 2016-08-24 江苏理工学院 Method for photocatalytic degradation of waste gas by electrodeless excimer lamp
CN105810552A (en) * 2015-02-27 2016-07-27 常州大恒环保科技有限公司 Short wave ultraviolet light generating method and device
CN105664679A (en) * 2016-01-13 2016-06-15 长沙上意电子科技有限公司 DBD plasma exhaust-gas treatment equipment
CN105536455B (en) * 2016-03-01 2017-09-15 常州大恒环保科技有限公司 A kind of industrial waste gas controlling device
CN106881013B (en) * 2017-04-12 2023-09-01 复旦大学 A device for decomposing trimethylamine malodorous gas

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