CN101810990B - Method for efficiently removing NOx in fume - Google Patents

Method for efficiently removing NOx in fume Download PDF

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Publication number
CN101810990B
CN101810990B CN2010101485872A CN201010148587A CN101810990B CN 101810990 B CN101810990 B CN 101810990B CN 2010101485872 A CN2010101485872 A CN 2010101485872A CN 201010148587 A CN201010148587 A CN 201010148587A CN 101810990 B CN101810990 B CN 101810990B
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China
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flue gas
electric cleaner
polar curve
electric
positive polarity
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CN2010101485872A
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CN101810990A (en
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朱天乐
孙轶斐
王美艳
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Beihang University
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Beihang University
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Abstract

The invention discloses a method for efficiently removing NOx in fume, which comprises the steps that based on a selective non-catalytic reduction principle, a part of NOx in the fume is reduced into N2 by urea or ammonia firstly in a boiler hearth or at the position of a flue close to an outlet of the hearth; then the fume enters an electric dust remover provided with a discharge plasma reaction unit or enters a special discharge plasma reactor after passing through a bag-type dust remover, and NO is oxidized into NO2 when realizing efficient dust removal; and finally the fume enters a wet-type absorption tower, and the NOx is further removed during efficient desulfuration. The method only needs to slightly reform the conventional fume purification processes of elective non-catalytic reduction denitration, electric dust removal or bag-type dust removal, and wet-type desulfurization, and then the NOx removal efficiency of more than 85%, the SO2 removal efficiency of more than 95% and the dust removal efficiency of more than 99% can be achieved under the condition that the investment and operation cost is slightly increased.

Description

A kind ofly efficiently remove NO in the flue gas xMethod
Technical field
The invention belongs to field of environment protection, relate to a kind of NO in the flue gas that efficiently removes xMethod, specifically, be meant a kind of through SNCR NO x, discharge plasma oxidation NO is NO 2With alkali lye absorption of N O xCombination, realize efficiently removing NO in the coal-fired flue-gas xMethod.
Background technology
The major pollutants of coal-fired flue-gas comprise flue dust, SO 2And NO xDeng.Utilize the denitration of SNCR or SCR technology earlier; Then, utilize electric cleaner or bag-type dust to separate flue dust; At last, utilizing the desulfurization of wet type desulfurizing system is conventional flue gas purifying method.
NO in the coal-fired flue-gas xMainly comprise NO and NO 2, wherein NO accounts for 95%.SCR is meant under the effect of catalyst, with NH 3Be reducing agent, optionally with flue gas in NO xReaction, and generate N 2And H 2O.SCR is a kind of gas denitrifying technology of maturation.At NH 3/ NO mol ratio is under 1 the situation, can obtain the NO more than 80% xRemoval efficiency.Yet SCR need consume a large amount of catalyst, and therefore investment and operating cost are high.Statistics shows that the catalyst costs of selective catalytic reduction system operating accounts for about the 30-50% of system's initial outlay usually, and its operating cost also is limited by life of catalyst.General every at a distance from 2 to 3 years, will change catalyst one time.At present the ability of China's autonomous production denitrifying catalyst with selective catalytic reduction is very limited, thereby popularization that should technology is restricted.In addition, for transforming unit, adopt the SCR technology also to have place restriction, problems such as equipment difficult installation.
SNCR is under the situation of not using catalyst, with NH 3, urea or other amino reductive directly spray into boiler furnace or near the flue of furnace outlet, in temperature is 800 ℃~1100 ℃ zone, reducing agent selectivity and NO xReaction makes it be reduced to N 2And H 2O.Usually, selective non-catalytic reduction system reasonable in design can reach the NO about 40% xRemoval efficiency.Compare with SCR, the SNCR operating cost is low, and rebuilding old equipment is few, is particularly suitable for transforming unit, and only needs ammoniacal liquor storage tank and injection apparatus, thereby investment is also much lower than SCR.But, the NO of SNCR xRemoval efficiency is lower, along with discharge standard is strict day by day, only relies on SNCR can not satisfy the discharge standard of increasingly stringent.
In fact, NO in flue gas 2Account for NO xRatio reach 50% when above, utilize conventional alkali lye desulphurization system, can realize efficiently removing NO xPurpose.Therefore, before flue gas gets into the alkali lye absorption desulfurizing system, utilize discharge plasma partial oxidation NO to be NO earlier 2, then, utilize conventional alkali lye desulphurization system to realize synchronized desulfuring and denitrifying, be efficiently to remove flue gas NO xOne of approach.But, the energy consumption of discharge plasma oxidation NO and NO concentration are closely related, when NO concentration is higher, only adopts discharge plasma oxidation and absorb the processing method that combines, and can cause energy consumption too high, are difficult to apply.In recent years, combine with absorption based on discharge plasma oxidation and remove SO 2And NO xThinking, Chinese scholars is done a lot, and has developed a kind of flue gas pollutant that is called catalytic oxidation like U.S. Powerspan company and has removed technology simultaneously, declares SO 2, NO xReach respectively more than 98%, 90% and 80% with the removal efficiency of Hg.But electrocatalysis oxidation reaction device power consumption height and complex structure that this technology is used, thereby investment and operating cost are all higher, the maintenance management difficulty is also big, is difficult to apply.In addition, the patent of domestic scholars application comprises that afflux light discharge plasma flue gas pollutant synchronous purification method (ZL200410029622.3), a kind of plasma fire coal boiler fume purification technology (ZL200310121117.7), resource remove the ozone oxidation dry method (CN101337152) of sulfur dioxide in flue gas, nitrogen oxide etc. simultaneously.It should be noted that these patented technologies all are based upon only to combine with absorption by plasma oxidation removes NO xImagination on, do not notice the high energy consumption that the NO oxidation is required.Just because of this, these technology all are not applied in coal-fired flue-gas purifies up to now.
Summary of the invention
The objective of the invention is to conventional flue gas treating process, i.e. SNCR denitration → electric precipitation or bag-type dust → wet desulfurizing process route, propose a kind of in electric cleaner the configuring plasma reaction member; Perhaps between sack cleaner and wet-type absorption tower, set up a special-purpose discharging plasma reactor, realize efficiently removing NO in the flue gas xMethod, both be applicable to the existing system transformation, also be applicable to the design and the construction of new system.Method provided by the invention can be little in the improvement project amount, and investment and operating cost are influenced under the little prerequisite, realizes SO in the flue gas 2, NO xWith efficiently removing of flue dust, SO 2, NO xReach respectively more than 95%, 85% and 99% with the removal efficient of flue dust.
The present invention proposes efficiently removes NO in the flue gas xMethod be based upon on the flue gas purifying technique route of SNCR denitration → electric precipitation or bag-type dust → wet desulphurization; Promptly has only this process route of employing; Again through configuring plasma reaction member in electric cleaner; Or between sack cleaner and wet-type absorption tower, set up special-purpose discharging plasma reactor, could realize efficiently removing NO in the flue gas xPurpose.Otherwise; If lack any one in SNCR and two links of wet flue gas desulfurization in the flue gas purifying technique; Or the wet-type absorption tower of flue gas desulfurization placed before electric cleaner or the special-purpose plasma reactor, all can't realize the purpose of efficient denitration of the present invention.
Described in electric cleaner the configuring plasma reaction member; Be the plasma reaction unit that the part electric field space of electric cleaner is transformed into the positive polarity streamer-discahrge, this reaction member can be positioned at arrival end, the port of export or the optional position, electric cleaner middle part of electric cleaner.Special-purpose plasma reactor then is one and is furnished with negative and positive the two poles of the earth, and adopts the reactor of positive polarity power supply power supply.In plasma reaction unit or special-purpose discharging plasma reactor, it is NO that the plasma that produces by electrion can make the NO efficient oxidation 2Simultaneously, it is charged that flue dust also takes place, and under the electric field force effect, the process of directional migration to pole plate or polar curve.
Wholely efficiently remove NO in the flue gas xProcess comprise following three key steps:
1) based on SNCR denitration principle, ammonia or urea and so on reducing agent is sprayed into boiler furnace or near the flue of boiler export, make its optionally with NO xEffect, reduction part NO xBe N 2
2) flue gas is discharged the back from boiler and is got into electric cleaner or sack cleaner, if adopt electric cleaner, then at the discharge plasma reaction member of electric cleaner, the Athermal plasma that produces based on the positive polarity streamer-discahrge is oxidized to NO with NO 2, meanwhile, in this reaction member, also there is the part flue dust charged, and directed movement under the electric field force effect, deposit on pole plate or the polar curve.Electric cleaner electric field region for not transforming still carries out dedusting in a conventional manner.
If adopt sack cleaner, then flue gas gets into special-purpose discharging plasma reactor from the boiler discharge and through after the sack cleaner.Likewise, in this special use discharging plasma reactor, the Athermal plasma that produces based on the positive polarity streamer-discahrge is oxidized to NO with NO 2Meanwhile, in this conversion zone, also there is the part flue dust charged, and directed movement under the electric field force effect, deposit on pole plate or the polar curve.
3) flue gas from electric cleaner or the discharge of special-purpose discharging plasma reactor gets into wet-type absorption tower, and this wet-type absorption tower is made absorption liquid with lime/lime stone slurries or other alkaline solution, effectively the SO in the absorbing and removing flue gas 2With NO with certain oxidizability x
Compare with traditional SNCR method denitration → electric precipitation or bag-type dust → wet desulphurization flue gas purifying method; The advantage of this method is only to need configuration discharge plasma reaction member in electric cleaner; Or between sack cleaner and wet-type absorption tower, set up special-purpose discharging plasma reactor; Than being provided with under catalytic-reduction denitrified the much little prerequisite of selectivity property, can make the acquisition of traditional flue gas purifying technique system efficiently remove NO in the flue gas in investment, operating cost xFunction.
Compare with discharge plasma that proposes in the prior art and the absorption method of multiple pollutant that combines in the smoke treatment; Advantage of the present invention is; Be fully recognized that the required energy consumption of oxidation NO is high; Under acceptable level of power consumption prerequisite, NO is difficult to realize this understanding by plasma oxidation flue gas middle and high concentration.Utilize selective non-catalytic reduction method to remove part NO earlier through design x, in the electric cleaner of being furnished with the discharge plasma reaction member or special-purpose discharging plasma reactor, oxidation NO is NO again 2Process program, evaded the energy consumption too high deficiency that the discharge plasma oxidation higher concentration NO exists.
Description of drawings
Fig. 1 is the technological process for flue gas purification sketch map that the correspondence that the present invention relates to adopts electric cleaner;
Fig. 2 is the technological process for flue gas purification sketch map that the correspondence that the present invention relates to adopts sack cleaner;
Fig. 3 to Fig. 5 is three kinds of arrangements being furnished with the electric cleaner of discharge plasma reaction member;
Fig. 6 is the sketch map of special-purpose discharging plasma reactor.
Among the figure:
1. boiler; 2. the electric cleaner of being furnished with the discharge plasma reaction member; 3. wet-type absorption tower; 4. chimney;
5. sack cleaner; 6. special-purpose discharging plasma reactor; 7. negative polarity high voltage source;
8. the conventional dedusting of electric precipitation is regional; 9. positive polarity high voltage source; 10. discharge plasma reaction member;
11. the polar curve of discharge plasma reaction member; 12. the pole plate of discharge plasma reaction member;
13. the polar curve of special-purpose discharging plasma reactor; 14. the pole plate of special-purpose discharging plasma reactor.
The specific embodiment
Below in conjunction with accompanying drawing and embodiment, to provided by the invention through configuration discharge plasma reaction member electric cleaner or special-purpose discharging plasma reactor be set between sack cleaner and wet type desulfurizing absorption tower realize that the method for efficient denitration describes.
When adopting electric cleaner, technological process for flue gas purification provided by the invention is as shown in Figure 1, and is specific as follows:
(1) with the burner hearth of ammonia or urea and so on injection of reducing agent to boiler 1 or near furnace outlet flue position, reducing agent optionally with NO xEffect makes part NO xBe reduced to N 2
(2) after flue gas is discharged from boiler 1, get into the electric cleaner 2 of being furnished with the discharge plasma reaction member, inducing the plasma oxidation NO of generation based on the positive polarity streamer-discahrge is NO 2Meanwhile, in this conversion zone, also there is a small amount of flue dust charged, and directed movement under the electric field force effect, deposit on pole plate or the printed line.In other zone of electric cleaner 2, conventional electric precipitation process takes place.
The flue gas of (3) discharging from electric cleaner 2 gets into wet-type absorption tower 3, and this wet-type absorption tower 3 adopts lime/lime stone slurries or other alkaline aqueous solution to make absorption liquid, effectively the SO in the absorbing and removing flue gas 2And NO x(NO 2Account for NO xRatio reach more than 50%).Last flue gas is discharged from chimney 4.
Step (2) is described be furnished with the discharge plasma reaction member electric cleaner 2 set inside discharge plasma reaction member 10, make it have oxidation NO function, like Fig. 3, Fig. 4 and shown in Figure 5.The pole plate 12 of discharge plasma reaction member 10 is identical with conventional electric precipitation zone 8 with the structural shape of polar curve 11, but the spacing of polar curve 11 and polar curve 11, polar curve 11 and pole plate 12 is less than conventional electric precipitation zone 8.
Among Fig. 3, discharge plasma reaction member 10 is arranged on the arrival end of electric cleaner 2, before the promptly conventional electric precipitation zone 8; Among Fig. 4, discharge plasma reaction member 10 is arranged on the port of export of electric cleaner 2, after the promptly conventional electric precipitation zone 8; Among Fig. 5, discharge plasma reaction member 10 is arranged on the middle part of electric cleaner, is about to conventional electric precipitation zone 8 and is divided into two parts, and the discharge plasma reaction member is between two conventional electric precipitation zones.Discharge plasma reaction member 10 is by 9 power supplies of positive polarity high voltage source; Conventional electric precipitation zone 8 is by 7 power supplies of negative polarity high voltage source.
When adopting bag-type dust, technological process for flue gas purification provided by the invention is as shown in Figure 2, and is specific as follows:
(1) with the burner hearth of ammonia or urea and so on injection of reducing agent to boiler 1 or near the furnace outlet position, reducing agent optionally with NO xEffect makes part NO xBe reduced to N 2
(2) after flue gas is discharged from boiler 1, get into sack cleaner 5, separate flue dust.
The flue gas of (3) discharging from sack cleaner 5 gets into special-purpose discharging plasma reactor 6.In special-purpose discharging plasma reactor 6, inducing the plasma oxidation NO of generation based on the positive polarity streamer-discahrge is NO 2Meanwhile, in this conversion zone, also there is a small amount of flue dust charged, and directed movement under the electric field force effect, deposit on pole plate or the printed line.
The flue gas of (4) discharging from special-purpose discharging plasma reactor 6 gets into wet-type absorption tower 3, and this wet-type absorption tower 3 adopts lime/lime stone or other alkaline aqueous solution to make absorption liquid, effectively the SO in the absorbing and removing flue gas 2And NO x(NO 2Account for more than 50% of NOx).Last flue gas is discharged from chimney 4.
Special-purpose discharging plasma reactor 6 is as shown in Figure 6.Special-purpose discharging plasma reactor 6 is by 9 power supplies of positive polarity high voltage source, and its pole plate 14 and polar curve 13 are identical with conventional electric cleaner 2, but the spacing of the spacing of polar curve 13 and polar curve 13, polar curve 13 and pole plate 14 is less than conventional electric cleaner.
Embodiment 1:
Discharge coal-fired flue-gas from boiler 1 (being furnished with urea selective non-catalytic reduction denitrating system), when boiler 1 spray urea, do not discharge NO in the flue gas xConcentration is 520mg/m 3When boiler 1 spray urea, discharge flue gas and contain 2700mg/m 3SO 2, 310mg/m 3NO xAnd 10.2g/m 3Flue dust, flow are 120000m 3/ h.After electric cleaner 2 (plasma reaction unit 10 is as shown in Figure 3 with the layout of conventional electric precipitation unit 8) and wet-type absorption tower 3 (adopting lime stone slurry to make absorption liquid), SO 2, NO xReduce to 135mg/m respectively with the concentration of flue dust 3, 73mg/m 3And 52mg/m 3SO 2, NO xBe respectively 95%, 86% and 99.5% with the removal efficient of flue dust.
Embodiment 2:
Discharge coal-fired flue-gas from boiler 1 (being furnished with urea selective non-catalytic reduction denitrating system), when boiler 1 spray urea, do not discharge NO in the flue gas xConcentration is 420mg/m 3When boiler 1 spray urea, discharge flue gas and contain 2220mg/m 3SO 2, 232mg/m 3NO xAnd 7.8g/m 3Flue dust, flow are 60000m 3/ h.After electric cleaner 2 (plasma reaction unit 10 is as shown in Figure 4 with the layout of conventional electric precipitation unit 8) and wet-type absorption tower 3 (adopting spent lye to make absorption liquid), SO 2, NO xReduce to 96mg/m respectively with the concentration of flue dust 3, 59mg/m 3And 34mg/m 3SO 2, NO xBe respectively 95.7%, 86% and 99.6% with the removal efficient of flue dust.
Embodiment 3:
Discharge coal-fired flue-gas from boiler 1 (being furnished with ammine selective non-catalytic reduction denitrating system), when boiler 1 spray ammonia, NOx concentration is not 490mg/m in the discharge flue gas 3When boiler 1 spray ammonia, discharge flue gas and contain 1890mg/m 3SO 2, 301mg/m 3NO xAnd 9.1g/m 3Flue dust, flow are 12000m 3/ h.After electric cleaner 2 (layout of plasma reaction unit and conventional electric precipitation unit is as shown in Figure 5) and wet-type absorption tower 3 (adopting lime slurry to make absorption liquid), SO 2, NO xReduce to 68mg/m respectively with the concentration of flue dust 3, 72mg/m 3And 65mg/m 3SO 2, NO xBe respectively 96.4%, 85.3% and 99.3% with the removal efficient of flue dust.
Embodiment 4:
Discharge coal-fired flue-gas from boiler 1 (being furnished with urea selective non-catalytic reduction denitrating system), when boiler 1 spray urea, NOx concentration is not 535mg/m in the discharge flue gas 3When boiler 1 spray urea, discharge flue gas and contain 2170mg/m 3SO 2, 327mg/m 3NO xAnd 9.8g/m 3Flue dust, flow are 72000m 3/ h.After sack cleaner 5, special-purpose plasma reactor 6 and wet-type absorption tower 3 (adopting spent lye to make absorption liquid), SO 2, NO xReduce to 58mg/m respectively with the concentration of flue dust 3, 71mg/m 3And 15mg/m 3SO 2, NO xBe respectively 97.3%, 86.7% and 99.8% with the removal efficient of flue dust.
Embodiment 5:
Discharge coal-fired flue-gas from boiler 1 (being furnished with ammine selective non-catalytic reduction denitrating system), when boiler 1 spray ammonia, NOx concentration is not 496mg/m in the discharge flue gas 3When boiler 1 spray ammonia, discharge flue gas and contain 1620mg/m 3SO 2, 302mg/m 3NO xAnd 10.6g/m 3Flue dust, flow are 15300m 3/ h.After sack cleaner 5, special-purpose plasma reactor 6 and wet-type absorption tower 3 (adopting lime slurry to make absorption liquid), SO 2, NO xReduce to 63mg/m respectively with the concentration of flue dust 3, 71mg/m 3And 25mg/m 3SO 2, NO xBe respectively 96.1%, 85.7% and 99.8% with the removal efficient of flue dust.

Claims (5)

1. one kind efficiently removes NO in the flue gas xMethod, it is characterized in that: at first,, ammonia or urea are sprayed onto boiler furnace or near the exhaust pass of burner hearth, make part NO in the flue gas based on the SNCR principle xBe reduced to N 2, x=1 wherein, 2; Then, flue gas gets into the electric cleaner of being furnished with the discharge plasma reaction member, or through after the sack cleaner, gets into special-purpose discharging plasma reactor, and when realizing high-effective dust-removing, the Athermal plasma of discharge generation makes the NO in the flue gas be oxidized to NO 2At last, flue gas gets into wet-type absorption tower, makes NO xBy further absorbing and removing; Described discharge plasma reaction member is that the part electric field space transformation of conventional electric cleaner is formed, and reforming content is the matching way of adjustment pole plate and polar curve, substitutes the high voltage source power supply of negative polarity with the high voltage source of positive polarity.
2. according to claim 1ly efficiently remove NO in the flue gas xMethod, it is characterized in that: described discharge plasma reaction member is positioned at the arrival end of electric cleaner; Perhaps be positioned at the port of export of electric cleaner; Perhaps be positioned at the middle part of electric cleaner.
3. according to claim 1ly efficiently remove NO in the flue gas xMethod; It is characterized in that: the pole plate of described special-purpose discharging plasma reactor is identical with conventional electric cleaner with polar curve; But the spacing of polar curve and polar curve spacing and polar curve and pole plate is less than conventional electric cleaner, and the high voltage source of employing positive polarity is the reactor power supply.
4. according to claim 1ly efficiently remove NO in the flue gas xMethod, it is characterized in that: the pole plate of described discharge plasma reaction member is identical with conventional electric cleaner with polar curve, but the spacing of polar curve and polar curve and polar curve and pole plate is less than conventional electric cleaner.
5. describedly efficiently remove NO in the flue gas according to claim 1 or 3 xMethod, it is characterized in that: the high voltage source of described positive polarity is the positive polarity DC high-voltage power supply; Or the high voltage source of positive polarity high direct voltage stack interchange; Or the pulse power of positive polarity.
CN2010101485872A 2009-12-31 2010-04-16 Method for efficiently removing NOx in fume Expired - Fee Related CN101810990B (en)

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CN200910244609 2009-12-31
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Publication number Priority date Publication date Assignee Title
CN102059050B (en) * 2010-11-30 2013-10-30 浙江大学 Low-temperature plasma smoke compound pollutant control method
CN102302893B (en) * 2011-06-20 2014-10-29 中国华能集团清洁能源技术研究院有限公司 Selective non-catalytic reduction and denitration method for circulating fluidized bed boiler
CN103212284A (en) * 2013-03-15 2013-07-24 孙琦 Method and device for combined removal of nitric oxide and sulfide in flue gas
CN105642080A (en) * 2015-12-31 2016-06-08 神华集团有限责任公司 Device and method for purifying flue gases
CN106390712A (en) * 2016-10-18 2017-02-15 苏州超等医疗科技有限公司 Wet plasma denitration treatment technology
CN106880996B (en) * 2017-03-28 2020-01-07 中国科学院广州能源研究所 Method for controlling emission of dust and nitric oxide in tail gas and device for implementing method
CN110124480A (en) * 2019-05-13 2019-08-16 山西晋浙环保科技有限公司 A kind of streamer-discahrge plasma electric dedusting remodeling method based on coal-burning power plant

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CN101244361A (en) * 2008-03-21 2008-08-20 清华大学 Method for accelerating selective non-catalytic reduction of nitrogen oxides
CN101555819A (en) * 2008-04-08 2009-10-14 三菱电机株式会社 Emission-control equipment

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CN1332030A (en) * 2000-06-08 2002-01-23 黄立维 Method for removing NOx from airflow
CN101244361A (en) * 2008-03-21 2008-08-20 清华大学 Method for accelerating selective non-catalytic reduction of nitrogen oxides
CN101555819A (en) * 2008-04-08 2009-10-14 三菱电机株式会社 Emission-control equipment

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