CN102872716A - Treating device for removing NOx by low-temperature plasma collaborative catalyst and treating method thereof - Google Patents

Treating device for removing NOx by low-temperature plasma collaborative catalyst and treating method thereof Download PDF

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Publication number
CN102872716A
CN102872716A CN2012103929307A CN201210392930A CN102872716A CN 102872716 A CN102872716 A CN 102872716A CN 2012103929307 A CN2012103929307 A CN 2012103929307A CN 201210392930 A CN201210392930 A CN 201210392930A CN 102872716 A CN102872716 A CN 102872716A
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reactor shell
catalyst
temperature plasma
low
treating apparatus
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陈明功
范旭
李广程
陈明强
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Anhui University of Science and Technology
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Anhui University of Science and Technology
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Abstract

The invention belongs to the technical field of nitric oxide removal, and particularly relates to a treating device for removing NOx by a low-temperature plasma collaborative catalyst and a treating method thereof. The treating device comprises a reactor shell, wherein the reactor shell is internally provided with a metal anode, and the outer side of the reactor shell is wrapped with a metal cathode; a catalyst is filled between the outer wall of the metal anode and the inner wall of the reactor shell, and corresponds to the metal cathode in position; the upper end and the lower end of the reactor shell are respectively provided with a sealing cover which is provided with a gas inlet and a gas outlet; one end of the metal anode is connected with a positive electrode of a direct-current high-voltage power supply, and the metal cathode is connected with a negative electrode of the direct-current high-voltage power supply or is grounded. The treating device has the advantages that catalytic reaction is carried out under room temperature without heating, so that the energy is greatly saved; and the treating device is small in volume, light in weight and convenient in use and is suitable for being installed and applied on cars. In addition, a plurality of treating devices also can be connected in series or in parallel so as to ensure the treating effect of nitric oxide.

Description

A kind of low-temperature plasma synergistic catalyst removal NO xTreating apparatus and processing method thereof
Technical field
The invention belongs to the removal of nitrogen oxide technical field, be specifically related to treating apparatus and the processing method thereof of a kind of low-temperature plasma synergistic catalyst removal NOx.
Background technology
Nitrogen oxide (NO x) compound that formed by nitrogen, two kinds of elements of oxygen, it is not only the main cause that acid rain forms, and can form photochemical fog with the reaction such as hydrocarbons, is one of Air Pollutants.Nitrogen oxide is mainly from coal-fired flue-gas (stationary source) and vehicle exhaust (moving source).Along with the industrial coal amount increases and the automobile pollution increase, it is discharged into the NO in the atmosphere xContent also rolls up thereupon.Therefore, by NO xThe environmental pollution that causes also more and more is subject to people's attention.
NO xWater-soluble and reactivity relatively poor, administer difficulty, specification requirement is high.NO commonly used xRemoval methods comprises selective catalytic reduction, SNCR method, electron beam irradiation method, active coke absorption method, urea method, ammonia process and cobalt ammonia solution removal method etc.NO xSCR (SCR) technology refers to make reducing agent preferentially and the NO in the waste gas in the presence of catalyst xReaction also makes it be reduced to N 2Catalytic process.At present, use NH 3Make reducing agent, at TiO 2-V 2O 5-WO 3NO under the catalyst action in the SCR waste gas xMake it to generate N 2, the method has been successfully applied to abroad administers fixed source pollution such as nitric plant's tail gas, power plant flue gas, heavy oil boiler waste gas etc.; For the treating tail gas of mobile pollution source such as automobile etc. at present ripe catalyst be with cordierite (2MgO2Al 2O 35SiO 2) ceramic honey comb is carrier, uses Al 2O 3And CeO 2Be coating, and be active component with noble metal, can remove simultaneously CO, HC and NO xThree-way catalyst.
The low temperature plasma catalysis that develops rapidly in recent years (non-thermal plasma catalysis) technology is one of effective ways of administering low concentration gas, and is furtherd investigate and develop.Relevantly both at home and abroad studies show that the low-temperature plasma synergistic catalytic action is compared and singlely do the time spent and can effectively strengthen removal of nitrogen oxide efficient.The people such as Stefan Broer take ammonia as reducing agent, adopt dielectric barrier discharge to produce low temperature plasma under 100~250 ℃, and and V 2O 5-WO 3/ TiO 2Catalyst action (contains 82%N in the simulated maneuver tail gas 2, 13%O 2, 5%H 2O, 500mg/m 3NO xAnd 500mg/m 3NH 3), when being lower than 140 ℃ without plasma treatment NO XAlmost do not remove; 70% NO is approximately arranged when additional agents barrier discharge before catalyzed conversion xBe reduced, this moment, temperature was lower than 100 ℃; NO and NO 2In catalytic reaction, coexist, strengthened the selective of catalytic reaction.The Liu Chang of University Of Tianjin is pretty to wait the people to prove that by X ray spectrum the interchange dielectric barrier discharge plasma can cause catalytic reaction in zeolite micropore, and plasma can not only reduce catalyst surface activation energy, but also the induced surface catalytic reaction.
Although low-temperature plasma synergistic catalytic eliminating NO XCatalyst type a lot, but mostly adopt precious metal catalyst, and need reducing agent, thereby cause NO XTo remove cost higher, NO simultaneously xRemoval efficiency also remain further to be improved.Therefore, along with NO XThe continuous aggravation of polluting, the succinct efficiently NO of research and development XThe catalyst that treating apparatus and low temperature active are stronger is a technical problem that need to be resolved hurrily, that be of great practical significance simultaneously.
Summary of the invention
One of purpose of the present invention provides the treating apparatus of a kind of low-temperature plasma synergistic catalyst removal NOx.This treating apparatus is to NO XTreatment effect better, and this treating apparatus is easy to miniaturization, is convenient to install and use at mobile automobile, manufacturing and the operating cost of this treating apparatus are all lower simultaneously.
For achieving the above object, the present invention has adopted following technical scheme: the treating apparatus of a kind of low-temperature plasma synergistic catalyst removal NOx, this device comprises the reactor shell of tubulose or tubular, be provided with the column of setting coaxial with it or bar-shaped metal anode in the reactor shell, the outer ring of reactor shell is wound with tabular or netted metallic cathode; Also be provided with solid catalyst in the described reactor shell, described catalyst is filled between metal anode outer wall and the reactor shell inwall, and the upper surface of catalyst is mutually concordant with the upper surface of metallic cathode, and the lower surface of catalyst is mutually concordant with the lower surface of metallic cathode; The upper/lower terminal place of described reactor shell is provided with the capping for sealing, be provided with gas feed in one of them capping, be provided with gas vent in another capping, at least one end of described metal anode passes capping and stretches out the outside in reactor shell; The end that described metal anode stretches out in the capping outside links to each other with the positive pole of DC high-voltage power supply, and metallic cathode links to each other or ground connection with the negative pole of DC high-voltage power supply.
The present invention can also be able to further realization by following technical measures:
Preferably, described reactor shell is quartz glass tube or earthenware, and described metal anode is copper rod or aluminium bar or iron staff or stainless steel bar, and described metallic cathode is copper coin net or aluminium expanded sheets or iron plate net or expanded metal lath, and described capping is sillicon rubber blocking.
Further, described catalyst is made by following steps:
1), the clay raw ore is purified
The sepiolite original ore powder that will contain attapulgite adds in the distilled water, the mass unit of described sepiolite original ore powder is in gram, the volume of distilled water is in milliliter, the quality of the sepiolite original ore powder that then adds and the volume ratio of distilled water are 5:3, stir 10min, the static upper strata suspension that pours out, vacuum filtration intermediate layer suspension then, the gained solid filter cake grinds 105 ℃ of lower oven dry;
2), acid activation
With the nitric acid of concentration 1.0~2.0 mol/L or hydrochloric acid activation through 1) the step solid material of withdrawing deposit and obtaining, the mass unit of described solid material is in gram, the volume of nitric acid or hydrochloric acid is in milliliter, and then the volume ratio scope of the quality of described solid material and nitric acid or hydrochloric acid is 1:5~1:15; Described solid material is immersed in 24~72h in nitric acid or the hydrochloric acid under 20~60 ℃; The gained material spends the ionized water cyclic washing to neutral after the acid activation, filters and obtains filter cake, and the gained filter cake grinds after the cooling naturally at 120 ℃ of temperature heat drying 4h;
3), modification
With step 2) in the material that makes at room temperature impregnated in 24h in the cerous nitrate solution, the mass concentration of cerium oxide is 4~8% in the described cerous nitrate solution; Then with material evaporation drying 4h in 60 ℃ of water-baths, and at 200~260 ℃ of lower roasting 6h, then be ground to 60 orders; Dipping, evaporation drying, roasting, grinding are 3~4 times so repeatedly; It is 2~10% Cu (NO that the solid material that grinding is obtained impregnated in mass concentration 3) 2In the solution, at 60 ℃ of lower evaporation drying 4h, dried solid material grinds to 230~250 orders, use mould compressing, and at 300~500 ℃ of lower heat-activated 5h, the particle volume that final powder is broken into setting gets final product again.
Further, in the described step 1), the quality of sepiolite original ore powder is 200g, and the volume of distilled water is 120ml.
In the described step 3), the diameter range of the described isopyknic spherical particles of particle volume with setting is 0.5~2.5mm.
Described step 2) in, acid activation can be by the data value in the table 1.
Table 1 acid activation tables of data
Annotate: the acid in the table 1 is hydrochloric acid or nitric acid.
As preferred version of the present invention, the internal diameter 27~32mm of described quartz glass tube or earthenware, wall thickness 2~3mm, length 120~360mm; Described metal anode is that external diameter is the stainless steel bar of 4~12mm; Described metallic cathode is the aluminium expanded sheets of thickness 1.6~2.4mm, and the axial length along reactor shell of aluminium expanded sheets is 60~320mm.
Another object of the present invention provide a kind of according to the aforementioned processing device to NO XThe processing method that removes, its technical scheme is as follows:
Described DC high-voltage power supply continuous discharge, and the discharge voltage of DC high-voltage power supply is 5~45KV, and discharge current is 0.01~0.4mA, and discharge power is 0.2~4W; The exhaust gas flow that enters reactor shell is 2~7L/min, and waste gas initial concentration scope is 100~360ppm, and the air speed scope is 6-12s -1
The present invention has following beneficial effect:
1), this treating apparatus can at room temperature carry out catalytic reaction, need not heating, thereby greatly saved the energy.
2), this treating apparatus volume is little, lightweight, easy-to-use, be suitable for automobile and install and use.Simultaneously, also can be according to situations such as the shape of vehicle-exhaust exhaust pipe, capacity variation, field conditions, and with a plurality for the treatment of apparatus serial or parallel connections, to guarantee the treatment effect of nitrogen oxide.
3), the catalyst among the present invention is take the acidifying attapulgite as carrier, attapulgite claims again palygorskite, is the moisture alumina magnesia silicate of a kind of crystalloid, typical molecular formula is: Mg 5[SiO 10] 2(OH) 24H 2O, be 2:1 type layer chain structure, wherein Mg is often by Al and Fe Partial Replacement, form two-layer silicon-oxy tetrahedron and press from both sides the octahedra construction unit that forms of a magnesia (aluminium) atom, wherein tetrahedral layer is continuous, and is octahedra discontinuous, between tetrahedral layer and octahedron, form the open channel that is parallel to chain direction, have special fibrous crystal form, inner duct is abundant, the large (125~210m of specific area 2/ g), has good absorption, store and helps catalysis, the special fibre structure of attapulgite, the unusual performances such as colloid, absorption and decolouring, be widely used in the fields such as chemical industry, light industry, agricultural, weaving, building materials, geological prospecting, casting, silicate industry, atomic energy industry, environmental protection and pharmacy, the good reputations such as " kings of thousand soil ", " soil of general-purpose " are arranged.
The present invention takes full advantage of Concave-convex clay rod ore deposit and the rare-earth ore resource of China's abundant, and adopting the pickling attapulgite is catalyst carrier, and prepares a kind of novel nitrogen oxide catalyst that removes with rare-earth element cerium and Cu oxide modification.But wherein use rare earth modified Effective Raise to NO in the diesel exhaust xAdsorption storage selective, improved reactant concentration and reactivity, also have simultaneously good anti-H 2O and SO 2Poison performance.The catalyst that the present invention makes also has advantages of take base metal (Cu) as catalytic activity point, thereby so that the operating cost of catalyst is lower.
4), under the synergy of catalyst that the present invention makes and low temperature plasma, not only can improve reactant activity, but also be conducive to gas absorption and catalytic reaction, because when low temperature plasma activates gas molecule, also with absorption and the activity function of further activated catalyst, make low-temperature plasma synergistic absorption, catalytic action, realize NO XEffective absorption, storage and catalytic reduction.
For the treating tail gas of mobile pollution source such as automobile etc., under the low temperature plasma invigoration effect, NO in the vehicle exhaust x, the exhaust gas constituents such as HC is further polarized and have taxis, so exhaust gas constituents can adsorb by effective as selective and store, and has that reaction is fast, vapour lock is little, simple to operate, operating cost is low, do not affect the characteristics such as engine performance.Because the micro-pore diameter of attapulgite is different, and its compound use can further be improved it to the adsorptive selectivity of gas with various composition.
5), the catalyst and the low-temperature plasma synergistic technology that adopt the present invention to make, but Effective Raise NO xRemoval efficiency, and do not produce accessory substance, the accessory substance that catalyst is optionally degraded and produced in the plasma reaction; Also can be applicable to remove the NO in fuel oil, coal-burning boiler and the Industrial Stoves tail gas xThe catalyst that makes of the present invention and low-temperature plasma synergistic are done the time spent PM2.5 are also had good clean-up effect in addition.
Description of drawings
Fig. 1,2 all is structural representations for the treatment of apparatus among the present invention.
The implication of label symbol is as follows among the figure:
1-gas feed, 2-metallic cathode, 3-reactor shell, 4-gas vent, 5-metal anode, 6-catalyst, 7-capping, 8-DC high-voltage power supply, 9-tail gas concentration on-line analysis device, 10-treating apparatus.
The specific embodiment
As shown in Figure 1, 2, reactor shell 3 is by quartz glass tube (or the earthenware of internal diameter 27~32mm, wall thickness 2~3mm, length 120~360mm, the same quartz glass tube of size) makes, the outer wall of reactor shell 3 coats thickness 1.6~2.4mm aluminium expanded sheets, described aluminium expanded sheets is metallic cathode 2, and aluminium expanded sheets is 60~320mm along the axial length range of reactor shell 3; In reactor shell 3 central authorities the stainless steel bar that external diameters are 4~12mm (or other electrode materials, such as copper, aluminium, the same stainless steel bar of external diameter) is installed, described stainless steel bar is metal anode 5; Solid catalyst 6 is seated in the reactor shell 3 between stainless steel bar and the aluminium expanded sheets, and the filling length L of catalyst 6 should be consistent with the axial length of aluminium expanded sheets; The two ends of reactor shell 3 also are capping 7 sealings with sillicon rubber blocking, and the reactor two ends are respectively arranged with gas feed 1 and gas vent 4.
Adopting stainless steel bar among the present invention is metal anode, its reason is that its secondary electron yield of different electrode materials is different, the secondary electron yield size is followed successively by: copper>aluminium>iron>steel, secondary electron yield is larger, and then to produce electron energy higher, discharging efficiency is larger, and its effect is relatively better.The present invention adopts stainless steel, copper or aluminum, and major consideration is common materials, easily obtains, and cost is not high.
The material of metallic cathode adopts aluminium expanded sheets among the present invention, and its reason not only relates to the secondary electron yield of metal, and selected aluminium is taken into account treatment effect and the material market price considers; Secondly, aluminium expanded metals but not aluminium sheet, the one, guarantee that the reactor processing and fabricating is convenient, the 2nd, the aluminium expanded sheets consumptive material is far smaller than aluminium sheet, is conducive to economical with materials.
Reactor shell 3 adopting quartz glass pipe or earthenwares, its reason are that the dielectric constant of quartz glass or pottery is higher, because the low-temperature plasma density that the high material of dielectric constant produces in discharge process is large, capacity usage ratio is high.Only have after voltage surpasses critical voltage, could puncture the air in the reactor, and produce low temperature plasma, the reaction that removes of nitrogen oxide is recurred.
The two concentric of stainless steel bar and aluminium expanded sheets is installed, and can improve like this utilization rate of discharge space, and improves the utilization rate of electric energy; The length of metal anode 5 and metallic cathode 2 is general relevant with discharge current, and polar curve is longer, reaches the needed electric current of stable discharging just larger, and the electric energy of consumption is also just larger.
The packed height of catalyst 6 must be consistent with the axial length of aluminium expanded sheets, because only have consistent guarantee catalyst 6 to be in the plasma space zone fully, like this could more effective performance catalyst and the cooperative effect of plasma, thus reach the more effective NO of removing XPurpose.
The filling thickness of catalyst 6 is relevant with the gas flow resistance with discharge voltage, if the thickness increase can suitably increase voltage to reach the stable discharging purpose.
Below by embodiment the preparation process of the catalyst 6 among the present invention is further described.
Catalyst Preparation Example 1
1), the clay raw ore is purified: get the 200g sepiolite and add 120ml distilled water, stir 10min; The static upper strata suspension that pours out is got the intermediate layer suspension; Vacuum filtration intermediate layer suspension, solid filter cake grinds 105 ℃ of lower oven dry;
2), acid activation: with the sepiolite after the hydrochloric acid activation purification of concentration 1.0 mol/L, the solid-to-liquid ratio of sepiolite and hydrochloric acid (g/ml) is 1:10, under 20 ℃ of conditions, soak 24h, then use the deionized water cyclic washing to neutral, filter to get filter cake, filter filter cake at 120 ℃ of temperature heat drying 4h, naturally grind after the cooling;
3) the pickling sepiolite sample 50g that obtains, modification: with step 2) at room temperature impregnated in (the cerium oxide mass concentration in the cerous nitrate solution is 4%) 24h in the cerous nitrate solution, evaporation drying 4h in 60 ℃ of water-baths then, at 200 ℃ of lower roasting 6h, then be ground to 60 orders, again so repeatedly dipping, evaporation drying, roasting, grinding 3 times, repeatedly to grind be for the large aggregated particle dispersion of catalyst to impregnation-calcination, makes it particle diameter, decentralization is better.
Utilize the own space geometry restriction of interaction and clay ore deposit in active rare-earth component and clay ore deposit, prepare particle size relatively evenly and the modified clay ore deposit adsorbent of high degree of dispersion.It is 2% Cu (NO that solid sample after step 3) gained oven dry ground impregnated in mass concentration 3) 2Solution, evaporation drying 4h under 60 ℃ of conditions, dried solid sample grinds to 240 orders, uses mould compressing again, heat-activated 5h in 300 ℃ of temperature ranges, being ground into equal-volume spherical particles diameter is the particle of 0.5mm again.
In order to improve the compressibility of catalyst fines with dried solid sample grinding to 240 orders first; And be ground into again suitable volume after compressing with mould, and be to satisfy different needs, the final grain diameter that obtains of pulverizing to determine as required.
Catalyst Preparation Example 2
1), the clay raw ore is purified: identical with embodiment 1;
2), acid activation: with the sepiolite behind the nitric acid Purification by activation of concentration 1.5 mol/L, the solid-to-liquid ratio of sepiolite and nitric acid (g/ml) is 1:10, under 20 ℃ of conditions, soak 36h, use again the deionized water cyclic washing to neutral, filter filter cake at 105 ℃ of temperature heat drying 4h, naturally grind after the cooling;
3), modification: gained pickling sample 50g at room temperature be impregnated in (mass content 8% of cerium oxide) 24h in the cerous nitrate solution, then evaporation 4h is dry in 60 ℃ of water-baths, at 200 ℃ of temperature range roasting 6h, then be ground to 60 orders, more so repeatedly dipping, evaporation drying, roasting, grinding 4 times;
Utilize the own space geometry restriction of interaction and clay ore deposit in active rare-earth component and clay ore deposit, prepare particle size relatively evenly and the modified clay ore deposit adsorbent of high degree of dispersion.Solid sample after the step 3) gained oven dry grinding be impregnated in the Cu (NO of mass concentration 8% 3) 2Solution, evaporation drying 4h under 60 ℃ of conditions, dried solid sample grinds to 250 orders, uses mould compressing again, heat-activated 5h in 400 ℃ of temperature ranges, being ground into equal-volume spherical particles diameter is the particle of 1.5mm again.
Catalyst Preparation Example 3
1), the clay raw ore is purified: identical with embodiment 1;
2), acid activation: with the sepiolite behind the nitric acid Purification by activation of concentration 1.0 mol/L, the solid-to-liquid ratio of sepiolite and nitric acid (g/ml) is 1:15, under 20 ℃ of conditions, soak 48h, use again the deionized water cyclic washing to neutral, filter filter cake at 120 ℃ of temperature heat drying 4h, naturally grind after the cooling;
3), modification: gained pickling sample 50g at room temperature be impregnated in (mass content 6% of cerium oxide) 24h in the cerous nitrate solution, evaporation drying in 60 ℃ of water-baths then, at 220 ℃ of temperature range roasting 6h, then be ground to 60 orders, dipping so repeatedly, evaporation drying, roasting, grinding 3 times;
Utilize the own space geometry restriction of interaction and clay ore deposit in active rare-earth component and clay ore deposit, prepare particle size relatively evenly and the modified clay ore deposit adsorbent of high degree of dispersion.Solid sample after the oven dry of step 3) gained be impregnated in the Cu (NO of mass concentration 10% 3) 2In the solution, evaporation drying 3h under 60 ℃ of conditions, dried solid sample grinds to 230 orders, uses mould compressing again, heat-activated 6h in 500 ℃ of temperature ranges, being ground into equal-volume spherical particles diameter is the particle of 1.0mm again.
Below by embodiment the processing procedure for the treatment of apparatus of the present invention is further described.
Treating apparatus embodiment 1
Reactor shell 3 is made by the quartz glass tube (dielectric constant 3.7~3.9) of internal diameter 27mm, wall thickness 2mm, length 120mm, and the aluminium expanded sheets that the quartz glass tube outer wall coats thickness 1.6mm is metallic cathode 2, the axial length 60mm of aluminium expanded sheets; In quartz glass tube central authorities external diameter 8mm stainless steel bar being installed is metal anode 5, and solid catalyst 6 is seated in the quartz glass tube between stainless steel bar and the aluminium expanded sheets, and the packed height of catalyst is 60mm, and catalyst is consistent with the relative position of aluminium expanded sheets; The two ends of reactor shell 3 seal with sillicon rubber blocking.Waste gas passes into conversion zone by the lower end of reactor shell 3, and is discharged by the upper end of reactor shell 3.
Described DC high-voltage power supply 8 is the high voltage source generator that links to each other with dc source, and the positive pole of high voltage source generator links to each other the aluminium expanded sheets ground connection in the treating apparatus with stainless steel bar in the treating apparatus.
Enter NO in the waste gas of quartz glass tube xInitial concentration is 100ppm, air speed 6s -1, electric current: 0.01mA; Discharge power: 0.47W; Gas flow: 2L/min.Dc source adopts battery, through high voltage source generator Control of Voltage at 16kV, continuous discharge, the purified gas that treated device 10 is discharged enters tail gas concentration on-line analysis device 9, experiment test also calculates NO xEffectively removal efficiency is 72%.
Treating apparatus embodiment 2
Reactor shell 3 is made by the quartz glass tube (dielectric constant 3.7~3.9) of internal diameter 32mm, wall thickness 3mm, length 240mm, and the aluminium expanded sheets that the outer wall of quartz glass tube coats thickness 2mm is metallic cathode 2, the axial length 200mm of aluminium expanded sheets; The stainless steel bar that external diameter 6mm is installed in the central authorities of quartz glass tube is metal anode 5, solid catalyst 6 is seated in the quartz glass tube between stainless steel bar and the aluminium expanded sheets, the packed height of catalyst 6 is 200mm, and catalyst 6 is consistent with the relative position of aluminium expanded sheets; Reactor shell 3 two ends seal with sillicon rubber blocking.Waste gas passes into conversion zone by the lower end of quartz glass tube, and is discharged by the upper end of quartz glass tube.
Described DC high-voltage power supply 8 is the high voltage source generator that links to each other with dc source, and the positive pole of high voltage source generator links to each other the aluminium expanded sheets ground connection in the treating apparatus with stainless steel bar in the treating apparatus.
Enter NO in the waste gas of quartz glass tube xInitial concentration is 260ppm, air speed 10s -1, electric current: 0.22mA; Discharge power: 1.6W; Gas flow: 4L/min.Dc source adopts battery, through high voltage source generator Control of Voltage at 30kV, continuous discharge.The purified gas that treated device 10 is discharged enters tail gas concentration on-line analysis device 9, and experiment test also calculates NO xEffectively removal efficiency is 83%.
Treating apparatus embodiment 3
Reactor shell 3 is made by the earthenware (dielectric constant 9~10) of internal diameter 32mm, wall thickness 3mm, length 360mm, and the aluminium expanded sheets that the outer wall of earthenware coats thickness 3mm is metallic cathode 2, the axial length 320mm of aluminium expanded sheets; In the central authorities of earthenware external diameter 8mm stainless steel bar being installed is metal anode 5, and solid catalyst 6 is seated in the earthenware between stainless steel bar and the aluminium expanded sheets, and the packed height of catalyst 6 is 320mm, and catalyst 6 is consistent with the relative position of aluminium expanded sheets; The two ends of reactor shell 3 seal with sillicon rubber blocking.Waste gas passes into conversion zone by the lower end of earthenware, and is discharged by the upper end of earthenware.
Described DC high-voltage power supply 8 is the high voltage source generator that links to each other with dc source, and the positive pole of high voltage source generator links to each other the aluminium expanded sheets ground connection in the treating apparatus with stainless steel bar in the treating apparatus.
Enter NO in the waste gas of earthenware xInitial concentration is 360ppm, air speed 12s -1, electric current: 0.4mA; Discharge power: 4W; Gas flow: 7L/min.Dc source adopts battery, through through high voltage source generator Control of Voltage at 40kV, continuous discharge, the purified gas that treated device 10 is discharged enters tail gas concentration on-line analysis device 9, experiment test also calculates NO xEffectively removal efficiency is 96%.

Claims (7)

1. the treating apparatus of a low-temperature plasma synergistic catalyst removal NOx, it is characterized in that: this device comprises the reactor shell (3) of tubulose or tubular, be provided with the column of setting coaxial with it or bar-shaped metal anode (5) in the reactor shell (3), the outer ring of reactor shell (3) is wound with tabular or netted metallic cathode (2); Also be provided with solid catalyst (6) in the described reactor shell (3), described catalyst (6) is filled between metal anode (5) outer wall and reactor shell (3) inwall, and the upper surface of catalyst (6) is mutually concordant with the upper surface of metallic cathode (2), and the lower surface of catalyst (6) is mutually concordant with the lower surface of metallic cathode (2); The upper/lower terminal place of described reactor shell (3) is provided with the capping (7) for sealing, be provided with gas feed in one of them capping, be provided with gas vent in another capping, at least one end of described metal anode (5) passes capping (7) and stretches out the outside in reactor shell (3); The end that described metal anode (5) stretches out in capping (7) outside links to each other with the positive pole of DC high-voltage power supply (8), and metallic cathode (2) links to each other or ground connection with the negative pole of DC high-voltage power supply (8).
2. the treating apparatus of low-temperature plasma synergistic catalyst removal NOx according to claim 1, it is characterized in that: described reactor shell (3) is quartz glass tube or earthenware, described metal anode (5) is copper rod or aluminium bar or iron staff or stainless steel bar, described metallic cathode (2) is copper coin net or aluminium expanded sheets or iron plate net or expanded metal lath, and described capping (7) is sillicon rubber blocking.
3. the treating apparatus of low-temperature plasma synergistic catalyst removal NOx according to claim 2 is characterized in that described catalyst (6) made by following steps:
1), the clay raw ore is purified
The sepiolite original ore powder that will contain attapulgite adds in the distilled water, the mass unit of described sepiolite original ore powder is in gram, the volume of distilled water is in milliliter, the quality of the sepiolite original ore powder that then adds and the volume ratio of distilled water are 5:3, stir 10min, the static upper strata suspension that pours out, vacuum filtration intermediate layer suspension then, the gained solid filter cake grinds 105 ℃ of lower oven dry;
2), acid activation
With the nitric acid of concentration 1.0~2.0 mol/L or hydrochloric acid activation through 1) the step solid material of withdrawing deposit and obtaining, the mass unit of described solid material is in gram, the volume of nitric acid or hydrochloric acid is in milliliter, and then the volume ratio scope of the quality of described solid material and nitric acid or hydrochloric acid is 1:5~1:15; Described solid material is immersed in 24~72h in nitric acid or the hydrochloric acid under 20~60 ℃; The gained material spends the ionized water cyclic washing to neutral after the acid activation, filters and obtains filter cake, and the gained filter cake grinds after the cooling naturally at 120 ℃ of temperature heat drying 4h;
3), modification
With step 2) in the material that makes at room temperature impregnated in 24h in the cerous nitrate solution, the mass concentration of cerium oxide is 4~8% in the described cerous nitrate solution; Then with material evaporation drying 4h in 60 ℃ of water-baths, and at 200~260 ℃ of lower roasting 6h, then be ground to 60 orders; Dipping, evaporation drying, roasting, grinding are 3~4 times so repeatedly; It is 2~10% Cu (NO that the solid material that grinding is obtained impregnated in mass concentration 3) 2In the solution, at 60 ℃ of lower evaporation drying 4h, dried solid material grinds to 230~250 orders, use mould compressing, and at 300~500 ℃ of lower heat-activated 5h, the particle volume that final powder is broken into setting gets final product again.
4. the treating apparatus of low-temperature plasma synergistic catalyst removal NOx according to claim 3, it is characterized in that: in the described step 1), the quality of sepiolite original ore powder is 200g, and the volume of distilled water is 120ml.
5. the treating apparatus of a kind of low-temperature plasma synergistic catalyst removal NOx according to claim 3 is characterized in that: in the described step 3), the diameter range of the described isopyknic spherical particles of particle volume with setting is 0.5~2.5mm.
6. the treating apparatus of each described low-temperature plasma synergistic catalyst removal NOx is characterized in that: the internal diameter 27~32mm of described quartz glass tube or earthenware, wall thickness 2~3mm, length 120~360mm according to claim 2~5; Described metal anode (5) is the stainless steel bar of 4~12mm for external diameter; Described metallic cathode (2) is the aluminium expanded sheets of thickness 1.6~2.4mm, and the axial length along reactor shell (3) of aluminium expanded sheets is 60~320mm.
7. the processing method of the treating apparatus of a low-temperature plasma synergistic catalyst removal NOx according to claim 1, it is characterized in that: described DC high-voltage power supply (8) continuous discharge, and the discharge voltage of DC high-voltage power supply (8) is 5~45KV, discharge current is 0.01~0.4mA, and discharge power is 0.2~4W; The exhaust gas flow that enters reactor shell (3) is 2~7L/min, and waste gas initial concentration scope is 100~360ppm, and the air speed scope is 6-12s -1
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