CN102908896B - Method for catalytically oxidizing NO by dielectric barrier discharge plasma modified catalyst - Google Patents
Method for catalytically oxidizing NO by dielectric barrier discharge plasma modified catalyst Download PDFInfo
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- CN102908896B CN102908896B CN201210430001.0A CN201210430001A CN102908896B CN 102908896 B CN102908896 B CN 102908896B CN 201210430001 A CN201210430001 A CN 201210430001A CN 102908896 B CN102908896 B CN 102908896B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 77
- 238000000034 method Methods 0.000 title claims abstract description 34
- 230000004888 barrier function Effects 0.000 title claims abstract description 22
- 230000001590 oxidative effect Effects 0.000 title abstract 2
- 230000003197 catalytic effect Effects 0.000 claims abstract description 39
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 37
- 230000004048 modification Effects 0.000 claims abstract description 35
- 238000012986 modification Methods 0.000 claims abstract description 35
- 239000011521 glass Substances 0.000 claims abstract description 22
- 239000003513 alkali Substances 0.000 claims abstract description 5
- 230000003647 oxidation Effects 0.000 claims description 36
- 229910052760 oxygen Inorganic materials 0.000 claims description 23
- 239000003595 mist Substances 0.000 claims description 21
- 239000007789 gas Substances 0.000 claims description 20
- 238000010521 absorption reaction Methods 0.000 claims description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- 230000008569 process Effects 0.000 claims description 6
- 229910001220 stainless steel Inorganic materials 0.000 claims description 6
- 239000010935 stainless steel Substances 0.000 claims description 6
- WSHADMOVDWUXEY-UHFFFAOYSA-N manganese oxocobalt Chemical compound [Co]=O.[Mn] WSHADMOVDWUXEY-UHFFFAOYSA-N 0.000 claims description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- 239000005030 aluminium foil Substances 0.000 claims description 3
- 239000010453 quartz Substances 0.000 claims description 3
- 239000003570 air Substances 0.000 claims description 2
- 239000006227 byproduct Substances 0.000 abstract description 9
- 239000000047 product Substances 0.000 abstract description 5
- 238000005265 energy consumption Methods 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 23
- 229910020647 Co-O Inorganic materials 0.000 description 21
- 229910020704 Co—O Inorganic materials 0.000 description 21
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 16
- 229910021529 ammonia Inorganic materials 0.000 description 8
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 8
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 229910001873 dinitrogen Inorganic materials 0.000 description 4
- 239000011572 manganese Substances 0.000 description 4
- 229940071125 manganese acetate Drugs 0.000 description 4
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 description 4
- 229910052697 platinum Inorganic materials 0.000 description 4
- 239000012286 potassium permanganate Substances 0.000 description 4
- 238000000967 suction filtration Methods 0.000 description 4
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 3
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000003546 flue gas Substances 0.000 description 3
- 229910052750 molybdenum Inorganic materials 0.000 description 3
- 239000011733 molybdenum Substances 0.000 description 3
- 229910052700 potassium Inorganic materials 0.000 description 3
- 239000011591 potassium Substances 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- 230000010718 Oxidation Activity Effects 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 239000003426 co-catalyst Substances 0.000 description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 239000008246 gaseous mixture Substances 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- MGWGWNFMUOTEHG-UHFFFAOYSA-N 4-(3,5-dimethylphenyl)-1,3-thiazol-2-amine Chemical compound CC1=CC(C)=CC(C=2N=C(N)SC=2)=C1 MGWGWNFMUOTEHG-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000000809 air pollutant Substances 0.000 description 1
- 231100001243 air pollutant Toxicity 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- MZZUATUOLXMCEY-UHFFFAOYSA-N cobalt manganese Chemical compound [Mn].[Co] MZZUATUOLXMCEY-UHFFFAOYSA-N 0.000 description 1
- 229910000428 cobalt oxide Inorganic materials 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000007430 reference method Methods 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
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- Catalysts (AREA)
- Exhaust Gas Treatment By Means Of Catalyst (AREA)
Abstract
The invention discloses a method for catalytically oxidizing NO by a dielectric barrier discharge plasma modified catalyst. The method comprises the steps of filling a catalyst into a dielectric barrier discharge plasma reactor to be modified; and placing the modified catalyst into a glass pipe type fixed bed reactor and introducing mixed gas to catalytically oxidize the NO into NO2. The modified catalyst has higher low-temperature catalytic activity and the NO catalytic oxidization efficiency can reach 75-85% at maximum; the cylindrical dielectric barrier discharge plasma reactor is adopted so as to be convenient for observing modification conditions of the catalyst; the actual operation is simple and the modification condition is easy to control; the energy consumption is lower; the modification time is shorter; the product NO2 can be absorbed by an alkali solution to obtain a byproduct and can be recycled; and the method is convenient for actual production and application and has a higher industrial application value.
Description
Technical field
The present invention relates to a kind of method of dielectric barrier discharge plasma modified catalyst catalytic oxidation NO, belong to dielectric barrier discharge plasma modified catalyst and be applied to atmosphere pollution purification techniques field.
Background technology
Along with the fast development of economy, the problem of environmental pollution that energy resource consumption brings is day by day serious.At present, whole world NO
xcome from the burning of fossil fuel more than 95% in discharge, and the NO discharged in flue gas
xin, NO accounts for 90% ~ 95%.Nitrogen oxide causes acid rain, and photochemical fog etc. destroy the Air Pollutants of ball ecological environment and infringement health.Therefore the pollution how eliminating nitrogen oxide is the problem that in environmental protection, attracts people's attention very much.
At present, removing the application of nitrogen oxide aspect more is SCR technology (SCR), but may cause secondary pollution and reaction temperature is also higher due to adding of ammonia.A kind of alternative method is that NO Catalytic Oxygen is changed into NO
2, i.e. selective catalytic oxidation (SCO), the NO after oxidation
2available alkali lye absorbs.This method is simple to operate, and cost is lower.But how at a lower temperature NO to be oxidized to NO
2become the key of this technology.Meanwhile, in recent years, dielectric barrier discharge plasma technique causes increasing researcher in the concern of catalyst field as a kind of new material modification method.
Patent application CN101773780A discloses a kind of method of depriving nitric oxide by plasma cooperating with low-temperature catalytic oxidation NO, it is characterized in that containing NO, O
2pending mist, air speed controls at 10000 ~ 60000h
-1between, activated by plasma reactor, the gaseous mixture after activation, by being equipped with the fixed bed reactors of manganese-base oxide catalyst, makes the NO in gaseous mixture
xquantitatively under 50 ~ 150 DEG C of conditions be oxidized to NO
2.Quantitative for NO can be converted into NO by this invention at a lower temperature
2, and to absorb further, non-secondary pollution, accomplished recycling treatment, and CO, CO in gas
2, SO
2the adverse effect of impurity composition is little, process NO
xconcentration range wide.But the method is plasma body cooperative catalytic oxidation NO, gas needs first to carry out plasma-activated, and the gas after activation carries out catalytic oxidation again, and implementation process is inconvenient to control, and practical operation is more loaded down with trivial details, and therefore industrial application value is not high.
Patent of invention CN101822945A discloses a kind of method of catalytic oxidation of nitric oxide with low-temperature plasma modified catalyst.Catalyst is placed in plasma reactor and carries out modification under certain condition, the low-temperature catalytic oxidation ability of catalyst significantly improves, at 50 ~ 150 DEG C, the conversion ratio of NO can reach about 80 ~ 86%, but at a lower temperature (50 DEG C ~ 100 DEG C), the NO catalytic oxidation efficiency lower (15% ~ 45%) of this catalyst; Plasma energy consumption higher (input voltage 10 ~ 70V) simultaneously, and modification time longer (5 ~ 6h).And, the plasma reactor that the method adopts is coaxial-type dielectric barrier discharge reactor, handled catalyst must be placed in the gap place between alundum tube and stainless steel electrode, palpus frequent dismounting reactor during process, operate extremely inconvenient, and outer wall is the modification situation that opaque alundum tube also cannot observe catalyst, and therefore, actual application value is not high.
Patent CN101822983A discloses a kind of catalyst of catalytic oxidation nitrogen oxides in effluent, take mesoporous silicon oxide as carrier, one or both mixtures of potassium, molybdenum are doping component, and platinum is active component, adopt catalyst prepared by equal-volume step impregnation method.Under this catalyst action, utilize the oxygen itself contained in flue gas, oxidation of nitric oxide is become to be easy to water-soluble nitrogen dioxide, improve the oxidizability of nitrogen oxides in effluent, the denitration of recycling alkali liquor absorption.Present invention process gained is significantly better than the platinum based catalyst that do not adulterate through the catalytic oxidation performance of the platinum based catalyst of potassium, molybdenum doping, and denitration efficiency is high; Under the catalysed oxidn of the platinum based catalyst of potassium, molybdenum doping, NO in flue gas after oxidation
xoxidizability is just between 45%-65%, and recyclable denitration by-product nitrite, realizes the resource of denitration product.But reaction temperature higher (200 DEG C), catalytic oxidation activity is lower, and preparation process is complicated, and cost is also higher.
Therefore, in order to realize efficient cryogenic catalytic oxidation of nitric oxide, need the method for modifying of exploitation catalyst further.
Summary of the invention
The object of the present invention is to provide a kind of method of dielectric barrier discharge plasma modified catalyst catalytic oxidation NO, have higher low temperature active through the catalyst that dielectric barrier discharge plasma is modified, NO catalytic oxidation is most effective reaches 75 ~ 85%.The present invention, by the modified condition (modified atmospheres, modification voltage, modification time) of control medium barrier discharge plasma, is intended to find out a kind of catalyst plasma modification condition being comparatively applicable to catalytic oxidation NO.
The method of dielectric barrier discharge plasma modified catalyst catalytic oxidation NO of the present invention comprises the steps:
(1) by manganese cobalt/cobalt oxide Mn-Co-O
xcatalyst is placed in plasma reactor and carries out modification, and modified atmospheres is a kind of in nitrogen, air, oxygen, processes 0.5 ~ 3h, obtain modified catalysts under output voltage 4 ~ 8kV condition;
(2) will containing NO, O
2and N
2mist by being equipped with the fixed bed reactors of the catalyst after plasma modification, at 50 ~ 250 DEG C, the NO in mist is oxidized to NO
2, gas enters ammonia absorption bottle subsequently, obtains byproduct ammonium nitrate recoverable.
In the present invention, plasma reactor adopts coaxial-type cylinder shape medium to stop reactor, the stainless steel high-field electrode of a diameter 3 ~ 5mm is inserted in the medium glass pipe of internal diameter 8 ~ 12mm, medium glass pipe outer wall wraps aluminium-foil paper as earth electrode, quartz core is positioned at the below of high-field electrode and is fixed on medium glass pipe, catalyst is placed on quartzy core, and cover completely in region of discharge, specifically see accompanying drawing 1.
NO, O in the present invention
2and N
2mist in the concentration of volume percent of NO be 0.05%, O
2concentration of volume percent be 3 ~ 5%, N
2for balanced gas, mist air speed is 30000 ~ 35000h
-1.
In the present invention, manganese cobalt oxide catalyst adopts conventional method preparation, mainly use for reference method disclosed in invention CN101530795: manganese acetate, potassium permanganate and cobalt nitrate are mixed, and fully grind 30 ~ 40min, to be placed in 70 ~ 90 DEG C of baking ovens isothermal reaction 36 ~ 48 hours, product spends deionized water 3 ~ 4 times, suction filtration, then use absolute ethanol washing 2 ~ 3 times, suction filtration; At 100 ~ 120 DEG C dry 8 ~ 12 hours, through compressing tablet, grind, sieve and make 40 ~ 60 object particles, obtain manganese cobalt oxide catalyst Mn-Co-O
x, wherein the mol ratio of manganese acetate and potassium permanganate is the mol ratio of 0.5 ~ 1:1, Mn:Co is 5 ~ 10:1;
The present invention is as follows relative to the advantage of prior art:
The present invention adopts cylinder shape medium to stop reactor, is discharge medium with glass tube, is convenient to the modification situation of observing catalyst; Practical operation is simple, need not dismantle reactor, and modified condition is easy to control; Energy consumption is lower; Modification time is shorter; The low-temperature catalytic activity of the catalyst under modified condition of the present invention is better, and modified catalyst has higher NO catalytic oxidation activity, and NO catalytic oxidation is most effective reaches 75% ~ 85%, improves 15% ~ 25% than the catalyst efficiency without plasma modification.Compare patent of invention CN101822945A, the catalyst that the present invention obtains under cryogenic (50 DEG C ~ 100 DEG C) NO catalytic oxidation efficiency improves 5% ~ 35%, and when higher temperature, (250 DEG C) improve 45% ~ 55%; Product NO simultaneously
2available alkali liquor absorption, obtains accessory substance, recoverable; Facilitate production application, there is higher industrial application value.
Accompanying drawing explanation
Fig. 1 dielectric barrier discharge plasma reactor schematic diagram;
Fig. 2 is the efficiency chart of manganese Co catalysts catalytic oxidation NO under different modified atmospheres condition that the inventive method obtains;
Fig. 3 is the manganese Co catalysts that obtains of the inventive method at different modification voltage, the efficiency chart of catalytic oxidation NO under the time;
In figure: 1 be high-field electrode, 2 are glass tubes, 3 are earth electrodes, 4 are quartzy cores, 5 are fixed covers, 6 are air inlets, 7 are gas outlets, 8 are ac high voltage sources, 9 are rubber stoppers, 10 is catalyst.
Detailed description of the invention
Below in conjunction with drawings and Examples, the present invention is described in further detail, but scope is not limited to described content.
embodiment 1:the method of dielectric barrier discharge plasma modified catalyst catalytic oxidation NO, concrete operations are as follows:
(1) catalyst preparing: manganese acetate, potassium permanganate and cobalt nitrate are mixed, and fully grinds 30min, to be placed in 70 DEG C of baking ovens isothermal reaction 48 hours, product spends deionized water 3 times, suction filtration, then uses absolute ethanol washing 3 times, suction filtration; Solid at 100 DEG C dry 12 hours, through compressing tablet, grinds, sieves and make 40 ~ 60 object particles, obtain manganese cobalt oxide catalyst Mn-Co-O
x, wherein the mol ratio of manganese acetate and potassium permanganate is the mol ratio of 2:3, Mn:Co is 9:1;
(2) by Mn-Co-O
xcatalyst is placed in plasma reactor and carries out modification, plasma adopts coaxial-type cylinder shape medium to stop reactor, the stainless steel high-field electrode 1 of a diameter 3mm is inserted in the medium glass pipe 2 of internal diameter 10mm, high-field electrode 1 is fixed in glass tube 2 by fixed cover 5 and rubber stopper 9, medium glass pipe outer wall wraps aluminium-foil paper as earth electrode 3, quartz core 4 is positioned at the below of high-field electrode 1 and is fixed on medium glass pipe, air inlet 6 and gas outlet 7 are arranged on the upper of glass tube 2, ac high voltage source 8 is connected with high-field electrode 1 and low-field electrode 3 respectively, catalyst 10 is filled in (see figure 1) on quartzy core 4.Modified condition is under nitrogen gas plasma, output voltage 8kV, and modification time is 1h, and the modified catalyst obtained is denoted as Mn-Co-O
x-N
2-8kV-1h;
(3) by the catalyst Mn-Co-O after plasma modification
x-N
2-8kV-1h is placed in glass pipe type fixed bed reactors, passes into NO, O
2, N
2mist, by programmed temperature control instrument control temperature at 50 ~ 250 DEG C, wherein, reactor inlet gas componant (percent by volume) NO 0.05%, O
23%, N
2for Balance Air, mist total flow is 200ml/min, and air speed is 35000h
-1, the catalytic oxidation efficiency of NO can reach the highest by 84% 175 DEG C time, specifically sees Fig. 2.Reacted gas enters the ammonia absorption bottle that mass fraction is 10%, obtains byproduct ammonium nitrate recoverable.
embodiment 2:the method of dielectric barrier discharge plasma modified catalyst catalytic oxidation NO, concrete operations are as follows:
(1) method for preparing catalyst is with embodiment 1, then by Mn-Co-O
xcatalyst is placed in plasma reactor and carries out modification, and plasma reactor configurations is identical with embodiment 1.Modified condition is under air plasma, output voltage 8kV, and modification time is 1h, and the modified catalyst obtained is denoted as Mn-Co-O
x-air-8kV-1h;
(2) by the catalyst Mn-Co-O after plasma modification
x-air-8kV-1h is placed in glass pipe type fixed bed reactors, passes into NO, O
2, N
2mist, by programmed temperature control instrument control temperature at 50 ~ 250 DEG C, wherein, reactor inlet gas componant (percent by volume) NO 0.05%, O
23%, N
2for Balance Air, mist total flow is 200ml/min, and air speed is 30000h
-1, the catalytic oxidation efficiency of NO can reach the highest by 80% 150 DEG C time, specifically sees accompanying drawing 2.Reacted gas enters the ammonia absorption bottle that mass fraction is 10%, obtains byproduct ammonium nitrate recoverable.
embodiment 3:the method of dielectric barrier discharge plasma modified catalyst catalytic oxidation NO, concrete operations are as follows:
(1) method for preparing catalyst is with embodiment 1, then by Mn-Co-O
xcatalyst is placed in plasma reactor and carries out modification.Plasma reactor configurations is with embodiment 1, and difference is that the internal diameter of medium glass pipe is 8mm, and the diameter of stainless steel high-field electrode is 3mm.Modified condition is under oxygen gas plasma, output voltage 8kV, and modification time is 1h, and the modified catalyst obtained is denoted as Mn-Co-O
x-O
2-8kV-1h;
(2) by the catalyst Mn-Co-O after plasma modification
x-O
2-8kV-1h is placed in glass pipe type fixed bed reactors, passes into NO, O
2, N
2mist, by programmed temperature control instrument control temperature at 50 ~ 250 DEG C, wherein, reactor inlet gas componant (percent by volume) NO 0.05%, O
25%, N
2for Balance Air, mist total flow is 200ml/min, and air speed is 35000h
-1, the catalytic oxidation efficiency of NO can reach the highest by 80% 175 DEG C time, specifically sees accompanying drawing 2.Reacted gas enters the ammonia absorption bottle that mass fraction is 10%, obtains byproduct ammonium nitrate recoverable.
embodiment 4:the method of dielectric barrier discharge plasma modified catalyst catalytic oxidation NO, concrete operations are as follows:
(1) catalyst preparation process is identical with embodiment 1.Subsequently, by Mn-Co-O
xcatalyst is placed in plasma reactor and carries out modification.Plasma reactor configurations is with embodiment 1, and difference is that the internal diameter of medium glass pipe is 12mm, and the diameter of stainless steel high-field electrode is 5mm.Modified condition is under nitrogen gas plasma, output voltage 6kV, and modification time is 1h, and the modified catalyst obtained is denoted as Mn-Co-O
x-N
2-6kV-1h;
(2) by the catalyst Mn-Co-O after plasma modification
x-N
2-6kV-1h is placed in glass pipe type fixed bed reactors, passes into NO, O
2, N
2mist, by programmed temperature control instrument control temperature at 50 ~ 250 DEG C.Wherein, reactor inlet gas componant (percent by volume) NO 0.05%, O
23%, N
2for Balance Air, mist total flow is 200ml/min, and air speed is 35000h
-1, the catalytic oxidation efficiency of NO can reach the highest by 76% 150 DEG C time, specifically sees accompanying drawing 3.Reacted gas enters the ammonia absorption bottle that mass fraction is 10%, obtains byproduct ammonium nitrate recoverable.
embodiment 5:the method of dielectric barrier discharge plasma modified catalyst catalytic oxidation NO, concrete operations are as follows:
(1) catalyst preparation process is identical with embodiment 1.Subsequently, by Mn-Co-O
xcatalyst is placed in plasma reactor and carries out modification.Plasma reactor is identical with embodiment 1.Modified condition is under nitrogen gas plasma, output voltage 4kV, and modification time is 1h, and the modified catalyst obtained is denoted as Mn-Co-O
x-N
2-4kV-1h;
(2) by the catalyst Mn-Co-O after plasma modification
x-N
2-4kV-1h is placed in glass pipe type fixed bed reactors, passes into NO, O
2, N
2mist, by programmed temperature control instrument control temperature at 50 ~ 250 DEG C.Wherein, reactor inlet gas componant (percent by volume) NO 0.05%, O
23%, N
2for Balance Air.Mist total flow is 200ml/min, and air speed is 35000h
-1.The catalytic oxidation efficiency of NO can reach the highest by 75% 150 DEG C time, specifically sees accompanying drawing 3.Reacted gas enters the ammonia absorption bottle that mass fraction is 10%, obtains byproduct ammonium nitrate recoverable.
embodiment 6:the method of dielectric barrier discharge plasma modified catalyst catalytic oxidation NO, concrete operations are as follows:
(1) catalyst preparation process is identical with embodiment 1.Subsequently, by Mn-Co-O
xcatalyst is placed in plasma reactor and carries out modification.Plasma reactor is identical with embodiment 1.Modified condition is under nitrogen gas plasma, output voltage 8kV, and modification time is 0.5h.The modified catalyst obtained is denoted as Mn-Co-O
x-N
2-8kV-0.5h;
(2) by the catalyst Mn-Co-O after plasma modification
x-N
2-8kV-0.5h is placed in glass pipe type fixed bed reactors, passes into NO, O
2, N
2mist, by programmed temperature control instrument control temperature at 50 ~ 250 DEG C.Wherein, reactor inlet gas NO 0.05%, O
23%, N
2for Balance Air.Mist total flow is 200ml/min, and air speed is 35000h
-1.The catalytic oxidation efficiency of NO can reach the highest by 80% 175 DEG C time, specifically sees accompanying drawing 3.Reacted gas enters the ammonia absorption bottle that mass fraction is 10%, obtains byproduct ammonium nitrate recoverable.
Claims (1)
1. a method for dielectric barrier discharge plasma modified catalyst catalytic oxidation NO, is characterized in that carrying out as follows:
(1) manganese cobalt oxide catalyst is placed in plasma reactor and carries out modification, modified atmospheres is the one in nitrogen, air, oxygen, processes 0.5 ~ 3h, obtain modified catalysts under output voltage 4 ~ 8kV condition;
(2) will containing NO, O
2and N
2mist by being equipped with the fixed bed reactors of the catalyst after plasma modification, at 50 ~ 250 DEG C, the NO in mist is oxidized to NO
2, product NO
2with alkali liquor absorption, recycle;
Described plasma reactor adopts coaxial-type cylinder shape medium barrier discharge reactor, the stainless steel high-field electrode of a diameter 3 ~ 5mm is inserted in the medium glass pipe of internal diameter 8 ~ 12mm, medium glass pipe outer wall wraps aluminium-foil paper as earth electrode, quartz core is positioned at the below of high-field electrode and is fixed on medium glass pipe, manganese cobalt oxide catalyst is placed on quartzy core, and covers completely in region of discharge;
Described NO, O
2and N
2mist in the concentration of volume percent of NO be 0.05%, O
2concentration of volume percent be 3 ~ 5%, N
2for balanced gas, mist air speed is 30000 ~ 35000h
-1.
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|---|---|---|---|
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|---|---|---|---|
| CN201210430001.0A CN102908896B (en) | 2012-11-01 | 2012-11-01 | Method for catalytically oxidizing NO by dielectric barrier discharge plasma modified catalyst |
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| CN107433132B (en) * | 2017-09-06 | 2020-09-25 | 哈尔滨工程大学 | Device and method for removing nitrogen oxides in tail gas of marine diesel engine |
| CN110493946A (en) * | 2019-09-23 | 2019-11-22 | 大连理工大学 | A kind of device that large area jet stream discharge plasma resin sorbent surface is modified |
| CN114377670B (en) * | 2021-12-10 | 2023-06-20 | 浙江大学 | Composite metal oxide catalyst for low-temperature SCR denitration and preparation method thereof |
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