CN1923337A - Boiler smoke gas multipollutant ozonization and simultaneous elimination device and method therefor - Google Patents

Boiler smoke gas multipollutant ozonization and simultaneous elimination device and method therefor Download PDF

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Publication number
CN1923337A
CN1923337A CNA2006100530893A CN200610053089A CN1923337A CN 1923337 A CN1923337 A CN 1923337A CN A2006100530893 A CNA2006100530893 A CN A2006100530893A CN 200610053089 A CN200610053089 A CN 200610053089A CN 1923337 A CN1923337 A CN 1923337A
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China
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mercury
nitrogen oxide
boiler smoke
boiler
multipollutant
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CNA2006100530893A
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Inventor
周俊虎
岑可法
刘建忠
王智化
杨卫娟
黄镇宇
周志军
程军
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HANGZHOU BAINENG TECHNOLOGY Co Ltd
Zhejiang University ZJU
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HANGZHOU BAINENG TECHNOLOGY Co Ltd
Zhejiang University ZJU
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Priority to CNA2006100530893A priority Critical patent/CN1923337A/en
Publication of CN1923337A publication Critical patent/CN1923337A/en
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    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02ATECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A50/00TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
    • Y02A50/20Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters

Abstract

The invention relates to a device for removing several pollutants of boiler smoke. Wherein, it comprises (1), before or after the static deduster of smoke channel, ejecting into ozone at low temperature section as 110-150Deg. C, while the ratio between ejected amount and nitrogen oxide is 1.1-2.0 and the reaction time is more then 0.5s; (3), feeding treated smoke into alkali washing tower to wash, and absorbing nitrogen oxide, sulfur oxide, mercury, chloride hydrogen, and hydrogen fluoride, adding H2S, Na2S, or NaHS into liquid grove to fix mercury. The invention can reach 80% denitrate efficiency and 95% desulfurizing efficiency, 80% demercuration efficiency, 95% antichloration defluorination efficiency, and oxidize the volatile organic pollutant.

Description

The boiler smoke gas multipollutant ozonization and simultaneous elimination devices and methods therefor
Technical field
The present invention relates to environmental protection technical field, refer more particularly to a kind of boiler smoke gas multipollutant ozonization and simultaneous elimination devices and methods therefor.
Background technology
The oxysulfide that produces in the using energy source process, nitrogen oxide have caused serious day by day harm to the atmospheric environment of China, and in addition trace heavy metals mercury Hg, HCl, HF and volatile organic contaminant VOC etc. endanger also paid more and more attention.Sulfur dioxide has been carried out large-scale improvement and control at present, the control of nitrogen oxide is also brought into schedule day by day, and mercury, chlorine, fluorine, volatile organic contaminant etc. explicitly call in the coal-burning boiler of China as yet.Along with the development of China's economic society and the enhancing of people's environmental protection consciousness, these pollutants certainly will will progressively be controlled.
Present existing desulfur technology can be divided into several classes such as dry method, semidry method and wet method.Dry method, semidry method investment operating cost is low, but often has the not high shortcoming of desulfuration efficiency, and extensive boiler combustion equipment such as station boiler etc. often can not reach environmental requirement.What station boiler extensively adopted at present is limestone/gypsum wet process of FGD technology (WFGD), and this method desulfuration efficiency height is stable, but exists water consumption big, waste discharge secondary pollution, investment and the more high shortcoming of operating cost.
The control technology of nitrogen oxide mainly contains two classes: the first generic stove combustion process control mode, mainly contain the low-NOx combustor technology, and OFA (Over fire air) technology, the low oxygen combustion technology, combustion technology etc. is controlled NO by the combustion process adjustment again xDischarging, can be with NO xBe controlled at medium emission level, general denitration efficiency is about 30~50%.But these technology cause combustion stability to descend easily on the one hand, and burner region forms local reduction atmosphere easily, cause ash fusion point to descend, and cause the pickup slagging scorification phenomenon of water-cooling wall, influence the normal safe operation of boiler.Along with the further raising of environmental requirement, be difficult to realize NO on the other hand xFurther emission control.The second class technology is a gas denitrifying technology, and countries use such as the present U.S., Japan, Europe technology the most widely are SCR technology (SCR).SCR technology denitration efficiency height, stable, but under the high grey deployment scenarios in the flue gas higher dust granules cause the problems such as wearing and tearing, obstruction of catalyst easily, the heavy metal in the flying dust can cause the poisoning of catalyst, operation and investment cost be costliness very.Environmental Protection in China work is started late, the control of sulfur dioxide just just begins, nitrogen oxide certainly will be brought into schedule from now on, if the thinking that adopts developed country to administer item by item, adopt the desulfurization of wet process of FGD WFGD device, the method of selectivity catalysis SCR denitration certainly will increase huge investment, operating cost, and some old units even have problems such as difficult arrangement, so developing low-cost, high efficiency while desulphurization denitration technology just seem particularly important.
Present mercury control method mainly contains active carbon adsorption, wet process of FGD (WFGD) device demercuration method and flying dust absorption demercuration method.Because coal-burning boiler mercury background concentration is lower, the active carbon consumption is big, and cost is higher.Wet flue gas desulfurizer only can effectively absorb divalence mercury, and element state mercury often accounts for more than 50%, and wet flue gas desulfurizer WFGD is powerless to element state mercury, and its demercuration efficient is totally on the low side.Flying dust absorption demercuration efficient is lower, still is in the laboratory research stage at present.And,, generally all be in no control state except that special high concentration occasions such as incinerator for the hydrogen chloride HCl in the boiler smoke and hydrogen fluoride HF and volatile organic contaminant VOC.
Removing technology simultaneously at the various pollutants of fume of studying at present has dry method while desulphurization denitration technology in the stove, and electro-catalysis removes technology etc. simultaneously.Wherein electro-catalysis removes technology removal efficiency height simultaneously, and operating cost is low, is becoming the focus of people's research.Present electro-catalysis technology comprises electron beam technology, pulsed discharge plasma technology, technology such as steam ammonia corona discharge activation.Mainly utilize the neutral molecule (N in high energy electron and the flue gas 2, O 2, H 2O etc.) collision produces some living radicals (O, OH, O 3, HO 2Deng), the SO in these free radicals and the flue gas 2And NO xMolecular reaction generates SO 3, high valence state nitrogen oxide, nitric acid, sulfuric acid etc. are at NH 3Generate byproducts such as ammonium sulfate, ammonium nitrate under the condition that exists.Advantage is a dry removal, does not produce waste water and dregs, and desulphurization denitration simultaneously, accessory substance can recyclings, and to Hg, VOC etc. also have certain removal efficiency.But because the free radical time-to-live is very short, the generation and the smoke reaction device of free radical need be united two into one, discharge at whole flue, and contain a large amount of N in the boiler smoke 2, CO 2, H 2Material such as O, dust, discharging condition is abominable, simultaneously N 2, CO 2Consume a large amount of input energy, cause capacity usage ratio low, overall operation expense costliness.
Summary of the invention
The objective of the invention is to discharge at whole flue at various electro-catalysis technology, the energy consumption problem of higher provides a kind of boiler smoke gas multipollutant ozonization and simultaneous elimination devices and methods therefor.
The boiler smoke gas multipollutant ozonization and simultaneous elimination device has boiler furnace, back-end ductwork, the alkali liquid washing tower that connects successively, alkali liquid washing tower top is provided with demister, alkali liquid washing tower bottom is provided with reservoir, alkali liquid washing top of tower and chimney join, alkali liquid washing tower bottom and nitrate sulphate crystal treating apparatus join, be connected to alkali lye and mercury stabilizing agent adding set on the tower wall on reservoir liquid level top, on back-end ductwork, be provided with electrostatic precipitator.
The boiler smoke gas multipollutant ozonization and simultaneous elimination method may further comprise the steps:
1) before or after the electrostatic precipitator on boiler flue, 110~150 ℃ of low-temperature zone spray into ozone, the nitrogen oxide molar ratio that sprays in ozone and the boiler smoke is 1.1~2.0, water-fast lower valency nitrogen oxide in the boiler smoke is oxidized into high valence state nitrogen oxide soluble in water, oxidizing sulfur dioxide generates sulfur trioxide, the element state mercury oxidation becomes divalence mercury soluble in water, volatile organic contaminant oxidative degradation, and the reaction time was at least 0.5 second.
2) will send in the alkali liquid washing tower washing through the rapid boiler smoke of handling of previous step, absorb high valence state nitrogen oxide, oxysulfide, mercury and hydrogen chloride, hydrogen fluoride in the flue gas simultaneously, in reservoir, add H 2S, Na 2S or NaHS mercury fixative make divalence mercury generate HgS precipitation, sulfate and nitrate condensing crystallizing.Alkali lye be in NaOH, potassium hydroxide, calcium hydroxide, calcium oxide, calcium carbonate or the ammoniacal liquor one or more.
The invention has the beneficial effects as follows: boiler smoke gas multipollutant ozonization and simultaneous elimination new method provided by the invention, can be in the desulfuration efficiency more than the denitration efficiency and 95% that reaches more than 80%, realize the oxidative degradation of demercuration efficient, the dechlorination and defluorination efficient more than 95% and the organic contamination of part volatility more than 80%, can satisfy the environmental requirement of increasingly stringent from now on.
Description of drawings
Fig. 1 is a boiler smoke gas multipollutant ozonization and simultaneous elimination device I structural representation;
Fig. 2 is a boiler smoke gas multipollutant ozonization and simultaneous elimination device II structural representation;
Among the figure: boiler furnace 1, blower fan 2, air dry decontamination device 3, ozone generating-device 4, electrostatic precipitator 5, back-end ductwork 6, reservoir 7, alkali liquid washing tower 8, demister 9, nitrate sulphate crystal treating apparatus 10, alkali lye and mercury stabilizing agent adding set 11, chimney 12.
The specific embodiment
The present invention is directed to local air or oxygen discharge produces and to spray into flue behind the ozone nitrogen oxide, oxysulfide, mercury, VOC etc. are carried out oxidation or degraded, afterbody removes simultaneously in conjunction with the wet scrubbing device, if wet desulphurization device being installed then can carry out effective combination with it, realize desulfurization, denitration, demercuration, dechlorination, defluorinate simultaneously, take off VOC.
O 3Extensively exist in electron beam, pulsed plasma discharge as a kind of of free radical, and O 3Life cycle is longer relatively, therefore can with little air or oxygen at first ionization generate O 3, send into boiler flue then, just can reduce the power consumption of system greatly, through estimation O 3Only need discharge and just can meet the demands the gas of total exhaust gas volumn about 3%.
As shown in the figure, the boiler smoke gas multipollutant ozonization and simultaneous elimination device has boiler furnace 1, back-end ductwork 6, the alkali liquid washing tower 8 that connects successively, alkali liquid washing tower top is provided with demister 9, alkali liquid washing tower bottom is provided with reservoir 7, alkali liquid washing top of tower and chimney 12 join, alkali liquid washing tower bottom and nitrate sulphate crystal treating apparatus 10 join, be connected to alkali lye and mercury stabilizing agent adding set 11 on the tower wall on reservoir liquid level top, on back-end ductwork 6, be provided with electrostatic precipitator 5.
The boiler smoke gas multipollutant ozonization and simultaneous elimination method may further comprise the steps:
1) before or after the electrostatic precipitator on boiler flue 65,110~150 ℃ of low-temperature zone spray into ozone, the nitrogen oxide molar ratio that sprays in ozone and the boiler smoke is 1.1~2.0, water-fast lower valency nitrogen oxide in the boiler smoke is oxidized into high valence state nitrogen oxide soluble in water, oxidizing sulfur dioxide generates sulfur trioxide, the element state mercury oxidation becomes divalence mercury soluble in water, volatile organic contaminant oxidative degradation, and the reaction time was at least 0.5 second.
2) will send in the alkali liquid washing tower 8 washing through the rapid boiler smoke of handling of previous step, absorb high valence state nitrogen oxide, oxysulfide, mercury and hydrogen chloride, hydrogen fluoride in the flue gas simultaneously, in reservoir, add H 2S, Na 2S or NaHS mercury fixative make divalence mercury generate the HgS precipitation, and sulfate and nitrate carry out condensing crystallizing.
Below in conjunction with the drawings and specific embodiments the present invention is described in further detail.
The NO of boiler smoke discharging xIn, NO accounts for more than 95%, and other is NO 2, N 2O etc., and NO is water insoluble, is one of gaseous contamination material that is difficult to handle, and the NO of high valence state 2, NO 3, N 2O 5Can generate HNO with the water reaction 2, HNO 3, very easily being removed by the wet scrubbing device, the mercury in the boiler smoke is divided into particulate form absorption mercury, element mercury and divalence mercury, and wherein the element state mercury in the gas phase accounts for more than 50% of gas phase total mercury, and water insoluble, volatile being difficult to of element state mercury effectively captures.By spraying into ozone, O in 110~150 ℃ of temperature ranges of boiler flue 3/ NO molar ratio gets 1.1 ~ 2.0, NO can be oxidized to high valence state material soluble in water, and element mercury is oxidized to divalence mercury, removes the oxidized degraded of part volatile organic contaminant, part SO by the wet scrubbing tower 2Oxidized generation SO 3, wet scrubbing is to SO 2Remove quite effective, SO 3Compare SO 2Easier dissolving and water, simultaneously also easy solution water of micro-HCl, HF cooperates the wet scrubbing device just can realize efficiently removing simultaneously of multiple pollutant at the ozone oxidation afterbody, denitration, demercuration efficient and to spray into ozone amount relevant.If be equipped with limestone/gypsum wet process of FGD equipment, then can carry out integrating the cost of reducing investment outlay with this method after the appropriate reconstruction to it.
Detailed process is: spray into ozone in 110~150 ℃ of temperature ranges of boiler back end ductwork, spraying into the position can be before or after electrostatic precipitator, and the ozone straying quatity is pressed O according to NO concentration in the flue gas 3/ NO mol ratio 1.1~2.0: 1 is chosen, and the nitrogen oxide after the oxidation, oxysulfide, divalence mercury, hydrogen chloride, hydrogen fluoride etc. remove by the wet scrubbing tower, and absorption liquid is an alkali lye, and absorption liquid is recycling, adds H in the absorption liquid 2S, Na 2Mercury such as S, NaHS stabilizing agent makes mercury generate stable mercuric sulphide HgS precipitation, sells behind the condensing crystallizings such as the sulfate of enrichment, nitrate, chloride, fluoride or further handles.Further specify below in conjunction with accompanying drawing:
Embodiment 1
As shown in Figure 1, after purifying, the air or oxygen drying sends into ozone generating-device with the preparation high-concentrated ozone, the preceding temperature of electrostatic precipitator was about 150 ℃ dust-laden flue after ozone was sent into air preheater, straying quatity requires to adjust constantly by ozone and nitrogen oxide molar ratio 1.1 according to flue gas nitrogen oxide concentration and removal efficiency, guarantees the 0.5s reaction time at least.Spout adopts perforated grill to spray, and the flue gas after the processing enters the alkali liquid washing tower after electrostatic precipitator, and absorption liquid is recycling, and flue gas is sent into smoke stack emission after wet scrubbing, demist.Scrubbing tower adopts alkali lye as absorbent, and scrubbing tower is spray column or packed tower.As the alkali lye of absorbent is in NaOH, potassium hydroxide, calcium hydroxide, calcium oxide, calcium carbonate or the ammoniacal liquor one or more, alkali lye is recycling, sulfate, the nitrate that absorbs carries out condensing crystallizing to be handled, replenish alkali lye simultaneously and add the mercury fixative, make mercury generate stable mercuric sulphide precipitation.
Embodiment 2
As shown in Figure 2, air or oxygen is sent into ozone generating-device with the preparation high-concentrated ozone, ozone is sprayed into behind the electric cleaner about 110 ℃ low cloud of dust road before the alkali liquid washing tower, the ozone straying quatity is according to flue gas nitrogen oxide concentration and the requirement of all contaminations removal efficiency, dynamically adjust by ozone and nitrogen oxide mol ratio 2.0, spray into a some position and guarantee that flue gas has time of staying more than the 0.5s apart from the scrubbing tower inlet.Spray to adopt the perforated grill shape to spray and measure and mix to strengthen, flue gas after the processing enters the alkali liquid washing tower and absorbs, atmosphere pollution materials such as nitrogen oxide, oxysulfide, mercury, chlorine, fluorine all can efficient absorption, the used alkali lye of alkali liquid washing tower can be one or more in NaOH, potassium hydroxide, calcium hydroxide, calcium carbonate or the ammoniacal liquor, absorption liquid recycles, certain density sulfate, nitrate carry out condensing crystallizing, replenish alkali lye simultaneously and add the mercury fixative, make divalence mercury generate the mercuric sulphide precipitation.
At last, it is also to be noted that what more than enumerate only is specific embodiments of the invention.Obviously, the invention is not restricted to above embodiment, many distortion can also be arranged.
The present invention can summarize with other the concrete form without prejudice to spirit of the present invention and principal character.Therefore, no matter from which point, above-mentioned embodiment of the present invention all can only be thought can not limit the present invention to explanation of the present invention, claims have been pointed out scope of the present invention, and scope of the present invention is not pointed out in above-mentioned explanation, therefore, in implication suitable and any change in the scope, all should think to be included in the scope of claims with claims of the present invention.

Claims (4)

1. boiler smoke gas multipollutant ozonization and simultaneous elimination device, it is characterized in that it has boiler furnace (1), back-end ductwork (6), the alkali liquid washing tower (8) that connects successively, alkali liquid washing tower top is provided with demister (9), alkali liquid washing tower bottom is provided with reservoir (7), alkali liquid washing top of tower and chimney (12) join, alkali liquid washing tower bottom and nitrate sulphate crystal treating apparatus (10) join, be connected to alkali lye and mercury stabilizing agent adding set (11) on the tower wall on reservoir liquid level top, on back-end ductwork (6), be provided with electrostatic precipitator (5).
2, a kind of use boiler smoke gas multipollutant ozonization and simultaneous elimination method as claimed in claim 1 may further comprise the steps:
1) before or after the electrostatic precipitator (5) on boiler flue (6), 110~150 ℃ of low-temperature zone spray into ozone, the nitrogen oxide molar ratio that sprays in ozone amount and the boiler smoke is 1.1~2.0, water-fast lower valency nitrogen oxide in the boiler smoke is oxidized into high valence state nitrogen oxide soluble in water, oxidizing sulfur dioxide generates sulfur trioxide, the element state mercury oxidation becomes divalence mercury soluble in water, volatile organic contaminant oxidative degradation, and the reaction time was at least 0.5 second.
2) will send in the alkali liquid washing tower (8) washing through the rapid boiler smoke of handling of previous step, absorb high valence state nitrogen oxide, oxysulfide, mercury and hydrogen chloride, hydrogen fluoride in the flue gas simultaneously, simultaneously adding H in reservoir (7) 2S, Na 2S or NaHS mercury fixative make divalence mercury generate the HgS precipitation, and the sulfate of absorption and nitrate carry out condensing crystallizing.
3, a kind of boiler smoke gas multipollutant ozonization and simultaneous elimination method according to claim 2 is characterized in that, described lower valency nitrogen oxide is mainly NO; Described high valence state nitrogen oxide is mainly NO 2, NO 3And N 2O 5
4, a kind of boiler smoke gas multipollutant ozonization and simultaneous elimination method according to claim 2 is characterized in that, described alkali lye be in NaOH, potassium hydroxide, calcium hydroxide, calcium oxide, calcium carbonate or the ammoniacal liquor one or more.
CNA2006100530893A 2006-08-23 2006-08-23 Boiler smoke gas multipollutant ozonization and simultaneous elimination device and method therefor Pending CN1923337A (en)

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CN100496672C (en) * 2007-04-30 2009-06-10 武汉凯迪电力环保有限公司 Wet flue gas desulfurizing and hydrargyrum-removing technology based on two-stage oxidation reaction and system thereof
CN100496675C (en) * 2007-04-30 2009-06-10 武汉凯迪电力环保有限公司 Simultaneous desulfurization and denitration wet ammonia flue gas cleaning technology and system thereof
CN100496676C (en) * 2007-04-30 2009-06-10 武汉凯迪电力环保有限公司 Wet ammonia flue gas cleaning technology simultaneously removing various pollutant and system thereof
CN101850212A (en) * 2010-05-25 2010-10-06 华南理工大学 Method for removing total mercury from coal burning smoke
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CN100496672C (en) * 2007-04-30 2009-06-10 武汉凯迪电力环保有限公司 Wet flue gas desulfurizing and hydrargyrum-removing technology based on two-stage oxidation reaction and system thereof
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CN102015070B (en) * 2008-04-25 2013-09-04 三菱重工业株式会社 System for treating discharge gas and method of removing mercury from discharge gas
CN101850212A (en) * 2010-05-25 2010-10-06 华南理工大学 Method for removing total mercury from coal burning smoke
CN101879404B (en) * 2010-07-12 2013-01-30 华东理工大学 Recycled flue gas desulfurization and denitration method
CN101879404A (en) * 2010-07-12 2010-11-10 华东理工大学 Recycled flue gas desulfurization and denitration method
CN101927124A (en) * 2010-08-17 2010-12-29 江苏中金环保科技有限公司 Flue gas denitrification method
US8409535B2 (en) 2010-11-03 2013-04-02 Calpine Corporation System and method for removing a contaminant from a gas stream
CN102078761A (en) * 2010-12-06 2011-06-01 李鹏举 Comprehensive flue gas desulfurization, mercury removal and denitration process and device
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