CN104028087B - A kind of method and device thereof removing dioxin in high-temperature flue gas - Google Patents
A kind of method and device thereof removing dioxin in high-temperature flue gas Download PDFInfo
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- CN104028087B CN104028087B CN201410235174.6A CN201410235174A CN104028087B CN 104028087 B CN104028087 B CN 104028087B CN 201410235174 A CN201410235174 A CN 201410235174A CN 104028087 B CN104028087 B CN 104028087B
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- flue gas
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- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 title claims abstract description 53
- 239000003546 flue gas Substances 0.000 title claims abstract description 53
- 238000000034 method Methods 0.000 title claims abstract description 26
- HGUFODBRKLSHSI-UHFFFAOYSA-N 2,3,7,8-tetrachloro-dibenzo-p-dioxin Chemical compound O1C2=CC(Cl)=C(Cl)C=C2OC2=C1C=C(Cl)C(Cl)=C2 HGUFODBRKLSHSI-UHFFFAOYSA-N 0.000 title 1
- KVGZZAHHUNAVKZ-UHFFFAOYSA-N 1,4-Dioxin Chemical compound O1C=COC=C1 KVGZZAHHUNAVKZ-UHFFFAOYSA-N 0.000 claims abstract description 80
- 239000002250 absorbent Substances 0.000 claims abstract description 80
- 230000002745 absorbent Effects 0.000 claims abstract description 80
- 150000002013 dioxins Chemical class 0.000 claims abstract description 36
- 238000001179 sorption measurement Methods 0.000 claims abstract description 36
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- 239000000428 dust Substances 0.000 claims abstract description 19
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- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 2
- 239000011733 molybdenum Substances 0.000 claims description 2
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- 239000010937 tungsten Substances 0.000 claims description 2
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- 206010028980 Neoplasm Diseases 0.000 description 2
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 2
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 2
- 239000000292 calcium oxide Substances 0.000 description 2
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 2
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- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
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- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
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- SYSQUGFVNFXIIT-UHFFFAOYSA-N n-[4-(1,3-benzoxazol-2-yl)phenyl]-4-nitrobenzenesulfonamide Chemical class C1=CC([N+](=O)[O-])=CC=C1S(=O)(=O)NC1=CC=C(C=2OC3=CC=CC=C3N=2)C=C1 SYSQUGFVNFXIIT-UHFFFAOYSA-N 0.000 description 1
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- NNFCIKHAZHQZJG-UHFFFAOYSA-N potassium cyanide Chemical compound [K+].N#[C-] NNFCIKHAZHQZJG-UHFFFAOYSA-N 0.000 description 1
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- Treating Waste Gases (AREA)
Abstract
The method removing dioxin in high-temperature flue gas disclosed by the invention, first removes flying dust by the flue gas after UTILIZATION OF VESIDUAL HEAT IN and chilling through the first cleaner; Then the dioxins adsorption tower containing absorbent is passed into, the dioxin in absorption and separation flue gas; Pass into the absorbent dust in the second cleaner removing flue gas again, fume emission after purification, the absorbent of the absorption that reaches capacity in the absorbent dust of the second cleaner recovery and dioxins adsorption tower is all sent into absorbent and reclaims reactor, and input ozone reaction decomposition dioxin, the absorbent of purification is sent into dioxins adsorption tower, recycles.The device implementing said method comprises two cleaners, and containing the dioxins adsorption tower of absorbent, absorbent reclaims reactor and ozone generator.The present invention absorbs dioxin together with the advantages of ozone promotion catalytic decomposition of dioxins absorbent, removes the dioxin in high-temperature flue gas with can realizing high efficiency low cost.
Description
Technical field
The present invention relates to processing method and the device of high-temperature flue gas, particularly relate to a kind of method and the device thereof that remove dioxin in high-temperature flue gas.
Background technology
Dioxin is that a class connects 2 tricyclic aromatic organic compounds formed by the phenyl ring that chlorine replaces by 2 or 1 oxygen atom, comprises polychlorinated dibenzo-2 and dislikes English and polychlorinated dibenzo, have 210 kinds of isomers/congeners.Dioxin is the highly stable lipophilicity solid chemical compound of a class, and its fusing point is higher, and decomposition temperature is greater than 700 DEG C, and pole is insoluble in water, dissolves in majority of organic solvent.Natural microbial degradation, hydrolysis and the photolysis molecular structure impact on dioxin is less, is difficult to natural degradation.Some isomers in dioxin are extremely toxic substances, and its acute toxicity is equivalent to 1000 times of potassium cyanide.A large amount of zooperies shows, the dioxin of very low concentrations just goes out lethal effect to Animal performance.The diseases such as dioxin also causes skin acne, has a headache, becomes deaf, melancholy, insomnia, and chromosome damage, heart failure, cancer etc. may be caused.Its greatest danger has irreversible teratogenesis, carcinogenic, mutagenic three causing toxicity.In addition, dioxin also affects reproductive function, disturbance endocrine system, be therefore known as " poison in century ".As height persistent pollutant, dioxin has strong compatibility to soil and bed mud, is easy to accumulate in biological tissues, and eventually through food chain a large amount of enrichment in human body, and accumulate with more stable form.Once dioxin concentration of (especially women and children) in human body reaches certain value, the genotoxicity himself had, immunotoxicity and Endocrine toxicity will cause disease of skin, viscera disease, cancer and deformed child, affect the survival and development of the mankind.
Dioxin is mainly not intended to generation in various pyroprocess, such as, in the flue gas of waste incineration, metal smelt, cinerator etc., and the dioxin often containing higher concentration.In view of the toxicity of dioxin, each state has all made strict restriction to the discharge of dioxin.In China, industrial waste incinerator is lower than 1.0ngI-TEQ/Nm
3, be lower than 0.5ngI-TEQ/Nm to the dioxin standard of medical waste incineration furnace
3.From 2008, the dioxin standard of Beijing brought up to 0.1ngI-TEQ/Nm comprehensively
3.The dioxin standard of developed country is normally lower than 0.1ngI-TEQ/Nm
3.Soon, the dioxin standard of the domestic waste incineration of China will become lower than 0.1ngI-TEQ/Nm
3.The formulation of stricter discharge standard, the common people, to the fast lifting of the attention rate of environmental protection, to operating and be about to the high temperature facilities such as the waste incineration facility that builds up, propose stern challenge.How cheap and effectively control the discharge of dioxin, become a difficult problem in the urgent need to address.
The emission control of dioxin in pyroprocess, well-known by controlling incineration temperature, on the basis of turbulivity and gas residence time, can also be suppressed by inhibitor that dioxin generates, three approach are eliminated in the decomposition of absorption and separation dioxin and dioxin, reduce the discharge of dioxin further.
Article 1, approach is in pyroprocess, add the inhibitor suppressing dioxin to generate.Such as, CN101725989A discloses one, and to be adopted as sulphur, sulphur coal, calcium oxide, calcium hydroxide or calcium carbonate be inhibitor, suppresses the method that in Refuse Incineration Process, dioxin generates.CN101485955 discloses a kind of troilite and rubbish being put in the lump in incinerator, by the method for dioxin generation in the addition suppression Refuse Incineration Process of control troilite.CN201419076 discloses the method by the control realization dioxin emission reducing to the sulphur composition in coal.
Article 2 approach adopts active carbon to absorb, and dioxin is separated from flue gas.CN201537442U disclose a kind of by flue gas, spray active carbon and calcium oxide and in venturi reactor with flue gas forced contact, absorb the device of the dioxin in flue gas.CN201949799U discloses a kind of device adopting two cloth bag control dioxin, sprays into lime, in second cloth bag, spray into active carbon by venturi reactor in first cloth bag.Improve active carbon and smoke contacts, reach the object effectively absorbing dioxin, and active carbon can reuse until dioxin saturated adsorption, reduces system operation cost.CN1246597 discloses by spraying into active carbon in flue gas, then will be adsorbed with the Activated carbon separation of dioxin out, delivers to the method that dioxin is eliminated in combustion chambers burn process.CN201997249U discloses the discharge adopting the method spraying into alkaline cooling fluid in flue gas to reduce dioxin.
Article 3 approach decomposes, and usually under the effect of catalyst, allows dioxin oxidation Decomposition at a lower temperature.Such as, CN1626277 discloses a kind of based on V
2o
5(WO
3, MoO
3) and TiO
2catalyst, at the temperature of 240-320 DEG C, can effectively remove the dioxin in flue gas.CN101559362 discloses first by TiO
2load is on volcanic rock, and then supported V
2o
5, at the temperature of 200-450 DEG C, effectively can remove dioxin.European patent (the patent No.: the catalyst removing dioxin 634206) is also with TiO
2load barium oxide.United States Patent (USP) (the patent No.: 5227356) disclosed catalyst active component is transition metal oxide and noble metal.Japan Patent (patent No.: 200024460 peace-11047592) disclosed catalyst activity component comprises the metal oxides such as V, W, Cu, Mn, Cr, Pd, Ru, Pt and noble metal, and catalyst carrier can be TiO
2, SiO
2, Al
2o
3, ZrO
2.Japan Patent (the patent No.: flat-11226397) disclosed catalyst is the oxide of the transition metal such as load V, W, Mo, Cu, Mn, Fe, Co, Cr, Ni on the activated carbon.Also catalyst active component and polytetrafluoroethylene fibre can be prepared into the filter bag with catalytic activity, as CN101580973, CN101255615 and the United States Patent (USP) (patent No.: 5620669).In addition, CN201921634U discloses and utilizes ultraviolet emission device activation photocatalyst coating, reaches the object of catalytic decomposition of dioxins.CN101485958 discloses a kind of photo catalysis reactor for dioxin in flue gas of degrading and method for activating photocatalyst.Recent discovery, ozone effectively can promote the catalytic decomposition of dioxin, and such as, CN102814108A discloses ozone effect and promotes the low-temperature decomposition of dioxin on metal oxide catalyst.
But above patent, all exists some obvious shortcomings, such as, adding inhibitor can cause other to pollute usually.Simple use active carbon absorbs dioxin technology, and not only active carbon is expensive, and absorbs the active carbon after dioxin and as hazardous waste, must process, or directly burns as fuel, and operating cost is high.Adopt catalysis filter bag technology, because pressure drop is too large, the flow velocity of flue gas is partially slow, and there is the problem of catalyst loss, adds operating cost equally.And catalytic decomposition technology faces equally that facility scale is huge, catalyst poisoning and need periodic replacement, flue gas needs to heat again, etc. problem.Even if adopt ozone to promote dioxin catalytic decomposition, face the facility scale still problem such as a large amount of use of huge, ozone and catalyst periodic replacement equally.
Summary of the invention
The object of this invention is to provide a kind of method removing dioxin in high-temperature flue gas and device thereof of high efficiency low cost.
The method removing dioxin in high-temperature flue gas of the present invention, is characterized in that first the flue gas after UTILIZATION OF VESIDUAL HEAT IN and chilling being passed into the first cleaner, the flying dust in removing flue gas; Then, the flue gas eliminating flying dust is passed into the dioxins adsorption tower containing absorbent, the dioxin in absorption and separation flue gas; Again by remove the flue gas after dioxin pass into second cleaner removing flue gas in absorbent dust, flue gas after the second cleaner purification is from air flue emission, the absorbent dust that second cleaner reclaims is sent into absorbent and is reclaimed reactor, reactor is reclaimed by also sending into absorbent containing the absorbent reaching dioxin saturated adsorption in the dioxins adsorption tower of absorbent, reactor input ozone is reclaimed to absorbent, reaction decomposes dioxin at 25 DEG C ~ 350 DEG C, the absorbent reclaiming reactor purification through absorbent is sent into dioxins adsorption tower, recycles.
In the present invention, described absorbent can be active carbon, CNT, the active carbon through metal oxide modified or the CNT through metal oxide modified, wherein metal oxide accounts for 0 ~ 50% of absorbent gross mass, and described metal oxide is one or more in the oxide of manganese, cerium, copper, vanadium, iron, molybdenum, tungsten, chromium or nickel.
Implement the above-mentioned device removing dioxin method in high-temperature flue gas, comprise the first cleaner, containing the dioxins adsorption tower of absorbent, second cleaner, absorbent reclaims reactor and ozone generator, the exhanst gas outlet of the first cleaner is connected with the gas approach of the dioxins adsorption tower containing absorbent, exhanst gas outlet containing the dioxins adsorption tower of absorbent is connected with the gas approach of the second cleaner, the exhanst gas outlet of the second cleaner is connected with chimney, discharging opening containing the dioxins adsorption tower of absorbent is connected with the charging aperture that absorbent reclaims reactor, the charging aperture that discharging opening and the absorbent of the second deduster reclaim reactor is connected, the discharging opening that absorbent reclaims reactor is connected with the charging aperture of the dioxins adsorption tower containing absorbent, absorbent reclaims reactor and is connected with ozone generator.
The first above-mentioned cleaner can be sack cleaner, electric cleaner, cyclone dust collectors or their combination.The second described cleaner also can be sack cleaner, electric cleaner, cyclone dust collectors or their combination.
In the present invention, the described dioxins adsorption tower containing absorbent can be fixed bed absorption tower, fluid bed absorption tower or thermopnore absorption tower.
Usefulness of the present invention is: absorbent is absorbed dioxin together with the advantages of ozone promotion catalytic decomposition of dioxins.Not only absorbent can recycle but also the temperature of dioxin catalytic decomposition is low, facility scale is little, operating cost is low.And when utilizing catalytic decomposition of ozone dioxin, the impact of other compositions in flue gas can not be subject to, thus remove the effect of the dioxin in high-temperature flue gas with reaching high efficiency low cost.The facility removing the dioxin in high-temperature flue gas of high efficiency low cost provided by the invention and method, be applicable to the efficient removal of dioxin in the high-temperature flue gas comprising waste incineration, smelting iron and steel, cement kiln, cinerator etc. and other volatile organic matter.
Accompanying drawing explanation
Fig. 1 is the device schematic diagram removing dioxin in high-temperature flue gas.
In figure: 1, the first cleaner, 2, dioxins adsorption tower containing absorbent, the 3, second cleaner, 4, absorbent reclaims reactor, 5, ozone generator.
Detailed description of the invention
The present invention is further illustrated below in conjunction with accompanying drawing
With reference to Fig. 1, the device removing dioxin method in high-temperature flue gas of the present invention comprises the first cleaner 1, containing the dioxins adsorption tower 2 of absorbent, second cleaner 3, absorbent reclaims reactor 4 and ozone generator 5, the exhanst gas outlet of the first cleaner 1 is connected with the gas approach of the dioxins adsorption tower 2 containing absorbent, exhanst gas outlet containing the dioxins adsorption tower 2 of absorbent is connected with the gas approach of the second cleaner 3, the exhanst gas outlet of the second cleaner 3 is connected with chimney, discharging opening containing the dioxins adsorption tower 2 of absorbent is connected with the charging aperture that absorbent reclaims reactor 4, the charging aperture that discharging opening and the absorbent of the second deduster reclaim reactor 4 is connected, the discharging opening that absorbent reclaims reactor 4 is connected with the charging aperture of the dioxins adsorption tower 2 containing absorbent, absorbent reclaims reactor 4 and is connected with ozone generator 5.Here the first cleaner 1 and the second cleaner 3 can be all sack cleaner, electric cleaner, cyclone dust collectors or their combination.Dioxins adsorption tower 2 containing active carbon can be fixed bed absorption tower, fluid bed absorption tower or thermopnore absorption tower.
During work, first the flue gas after UTILIZATION OF VESIDUAL HEAT IN and chilling passes into the first cleaner, filters the particles such as the flying dust removed in flue gas in the first cleaner; Then enter the dioxins adsorption tower containing absorbent, allow absorbent fully contact with flue gas, the dioxin in effective absorption and separation flue gas.The absorbent dust containing dioxin utilizing the second cleaner trap filter to escape from dioxins adsorption tower, reaches the flue gas of the discharge standard of country from air flue emission after purification.The absorbent dust collected from the second cleaner is sent into absorbent recovery reactor.Adsorb dioxin in dioxins adsorption tower to reach the saturated absorbent of absorption and be also fed to absorbent and reclaim in reactor.The ozone input absorbent produced by ozone generator reclaims reactor, reacts, utilize the super oxidability of ozone and the catalytic activity of absorbent, the dioxin be adsorbed on absorbent is thoroughly decomposed at 25 DEG C ~ 350 DEG C.Dioxins adsorption tower sent into by absorbent after process, recycles.
Claims (5)
1. remove a method for dioxin in high-temperature flue gas, it is characterized in that first the flue gas after UTILIZATION OF VESIDUAL HEAT IN and chilling being passed into the first cleaner, the flying dust in removing flue gas; Then, the flue gas eliminating flying dust is passed into the dioxins adsorption tower containing absorbent, the dioxin in absorption and separation flue gas; Again by remove the flue gas after dioxin pass into second cleaner removing flue gas in absorbent dust, flue gas after the second cleaner purification is from air flue emission, the absorbent dust that second cleaner reclaims is sent into absorbent and is reclaimed reactor, reactor is reclaimed by also sending into absorbent containing the absorbent reaching dioxin saturated adsorption in the dioxins adsorption tower of absorbent, reactor input ozone is reclaimed to absorbent, reaction decomposes dioxin at 25 DEG C ~ 350 DEG C, the absorbent reclaiming reactor purification through absorbent is sent into dioxins adsorption tower, recycles; Above-mentioned absorbent is active carbon, CNT, the active carbon through metal oxide modified or the CNT through metal oxide modified, wherein metal oxide accounts for 0 ~ 50% of absorbent gross mass, and described metal oxide is one or more in the oxide of manganese, cerium, copper, vanadium, iron, molybdenum, tungsten, chromium or nickel.
2. implement the claims the device removing dioxin method in high-temperature flue gas described in 1, it is characterized in that comprising the first cleaner (1), containing the dioxins adsorption tower (2) of absorbent, second cleaner (3), absorbent reclaims reactor (4) and ozone generator (5), the exhanst gas outlet of the first cleaner (1) is connected with the gas approach of the dioxins adsorption tower (2) containing absorbent, exhanst gas outlet containing the dioxins adsorption tower (2) of absorbent is connected with the gas approach of the second cleaner (3), the exhanst gas outlet of the second cleaner (3) is connected with chimney, discharging opening containing the dioxins adsorption tower (2) of absorbent is connected with the charging aperture that absorbent reclaims reactor (4), the charging aperture that discharging opening and the absorbent of the second deduster reclaim reactor (4) is connected, the discharging opening that absorbent reclaims reactor (4) is connected with the charging aperture of the dioxins adsorption tower (2) containing absorbent, absorbent reclaims reactor (4) and is connected with ozone generator (5).
3. the device removing dioxin method in high-temperature flue gas according to claim 2, is characterized in that described the first cleaner (1) is sack cleaner, electric cleaner, cyclone dust collectors or their combination.
4. the device removing dioxin method in high-temperature flue gas according to claim 2, is characterized in that described the second cleaner (3) is sack cleaner, electric cleaner, cyclone dust collectors or their combination.
5. the device removing dioxin method in high-temperature flue gas according to claim 2, is characterized in that the described dioxins adsorption tower (2) containing absorbent is fixed bed absorption tower, fluid bed absorption tower or thermopnore absorption tower.
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