CN1762551A - The method of desulfurizing and denitrifying flue gas by electron beam and device thereof - Google Patents
The method of desulfurizing and denitrifying flue gas by electron beam and device thereof Download PDFInfo
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- CN1762551A CN1762551A CN 200510025131 CN200510025131A CN1762551A CN 1762551 A CN1762551 A CN 1762551A CN 200510025131 CN200510025131 CN 200510025131 CN 200510025131 A CN200510025131 A CN 200510025131A CN 1762551 A CN1762551 A CN 1762551A
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Abstract
The invention discloses a kind of method of desulfurizing and denitrifying flue gas by electron beam, it mainly is to spray into oxidizing agent solution before the irradiation reaction of prior art.The present invention also discloses a kind of device of desulfurizing and denitrifying flue gas by electron beam, and it mainly is provided with the nozzle system that at least one is used to spray oxidizing agent solution at the irradiated site front end of the radiation reactor of existing apparatus.The present invention has advantages such as the construction costs that improves sulfur dioxide and removal efficiency of nitrogen oxides or reduce the desulfurizing and denitrifying flue gas by electron beam purifier and power consumption.
Description
Technical field
The present invention relates to filed of flue gas purification, design a kind of method and device thereof of handling the desulfurizing and denitrifying flue gas by electron beam of sulfur dioxide in flue gas that coal-burning boiler produces and nitrogen oxide especially.
Background technology
Brought severe contamination by the sulfur dioxide that flue gas contained that coal-burning boiler produced and the discharging of nitrogen oxide to atmospheric environment, sulfur dioxide and nitrogen oxide also are the main atmosphere pollutions that produces acid rain, so the importance that the purification work of the flue gas desulfurization and denitrification present environmental contaminants that are China are administered.
The desulfurizing and denitrifying flue gas by electron beam technology is the coal-fired flue-gas process for purifying that a kind of new development is got up, and this technology has developed into the starting stage of commercial Application at present.Fig. 1 is the apparatus structure schematic diagram of existing desulfurizing and denitrifying flue gas by electron beam, the method treatment process of its desulphurization denitration is that the flue gas that earlier coal-burning boiler 1 is produced is sent into flue gas pretreater 3 through first flue 2, on this pre-flue gas pretreater 3 first nozzle system is installed, can spray cooling water makes the flue gas cool-down humidification to removing the suitable condition that reaction is carried out, again flue gas is sent in the irradiation reaction device 8 of irradiation reaction system 78 through second flue 6, this irradiation reaction system 78 is made up of irradiation reaction device 8 and electron accelerator system 7, and pipeline 5 is installed on this second flue 6, can make flue gas before entering irradiation reaction device 8, add certain stoichiometric ammonia, the mixed flue gas electron beam irradiation of drawing subsequently by the electron accelerator system 7 on the irradiated site 81 that is installed in irradiation reaction device 8, after series of chemical, sulfur in smoke and nitrogen oxide generate ammonium sulfate and ammonium nitrate product, collect these products through the 3rd flue 9 and with accessory substance gatherer 10 together with the flue gas after handling, and with it as agrochemical, together the flue gas after the processing that the 3rd flue 9 and accessory substance gatherer 10 come out enters atmosphere (referring to document 1: the honor of Tai moral by chimney 12 behind the 4th flue 11, Han Binbing, Chengdu power plant electron beam flue gas desulfurization demonstration project, China Power, 1998, Vol 31 (11): 42-47; Document 2:Andrzej G.Chmielewski, Janusz Licki, AndrejPawelec, Bogdan Tyminski, Zbigniew Zimek, Operational experience of theindustrial plant for electron beam flue gas treatment, 71 (2004): 439-442).
The basic principle of above-mentioned technology is: the N in factory's smoke evacuation
2, O
2With the institute water content behind high-energy electron beam irradiation, produce a large amount of OH, O, HO
2Deng oxyradical, SO in these free radicals and the flue gas
2And NO
xProduce oxidation reaction and generate H
2SO
4And HNO
3, the vaporific H that is generated
25O
4And HNO
3With the NH in the injecting reactor
3Interacting generates the ammonium sulfate and the ammonium nitrate of white powdery, and ammonium sulfate and ammonium nitrate can directly be used as agrochemical as final accessory substance.
Existing desulfurizing and denitrifying flue gas by electron beam technology exists following problem: (1) desulphurization denitration carries out in a device simultaneously, can not take into account the differential responses characteristic of desulfurization and denitration, reaction temperature for example, removal effect especially denitration effect is not ideal enough, this is because general chilling temperature 60-65 ℃ of adopting when the flue gas cool-down humidification of prior art more is partial to desulphurization reaction, and nitrogen oxide remove the living radical that mainly depends on electron beam irradiation and produced.(2) energy consumption of electron accelerator is bigger, and as reaching higher desulfurization degree and denitration rate, required electron accelerator power ratio is bigger.
Goal of the invention
To the objective of the invention is in order solving the problems of the technologies described above, a kind of method and device thereof of desulfurizing and denitrifying flue gas by electron beam to be provided.
One of purpose of the present invention is to realize by following technical proposals:
A kind of method of desulfurizing and denitrifying flue gas by electron beam, it comprises the following steps:
1) the flue gas cool-down humidification that contains sulfur dioxide, nitrogen oxide that boiler is produced;
2) adding ammonia mixes with flue gas;
3) mixed flue gas is carried out electron beam irradiation and react, thereby make sulfur in smoke, nitrogen oxide generate ammonium sulfate and ammonium nitrate and be removed, realized gas cleaning;
The inventive method also before the reaction of the electron beam irradiation of step 3), in flue gas, spray into oxidizing agent solution.
Wherein, this oxidant is preferably peroxide.
For example be selected from hydrogen peroxide, potassium peroxide, sodium peroxide, ammonium persulfate, sodium peroxydisulfate and the potassium peroxydisulfate etc. one or more.
This flue gas volume and the preferable 10000Nm of being chosen as of oxidizing agent solution mass ratio that is sprayed into
3: 20-180kg, and in this oxidizing agent solution the mass ratio of oxidant and water preferable be 1: 50-4000.
The size droplet diameter of the oxidizing agent solution that the present invention sprayed into is generally 20～200 μ m below 200 μ m.As everyone knows, size droplet diameter is more little, and surface area is big more, and effect is good more concerning chemical reaction.
In the present invention's one preferable example, described in flue gas, spray into oxidizing agent solution be meant with the mixed flue gas of ammonia in spray into.
Another object of the present invention is to realize by following technical proposals:
A kind of device of desulfurizing and denitrifying flue gas by electron beam, it includes first flue that links to each other with boiler; The flue gas pretreater that links to each other with this flue is equipped with first nozzle system that damping water is cooled off in ejection on this flue gas pretreater; One end and second flue that this flue gas pretreater links to each other which is provided with the pipeline that sprays ammonia; The irradiation reaction system that is connected with the other end of this second flue, this irradiation reaction system includes electron accelerator system and the irradiation reaction device that produces electron beam and carry out the electron beam irradiation reaction, and this electron accelerator system is installed on the irradiated site top of irradiation reaction device; It is characterized in that this device is provided with the nozzle system that at least one is used to spray oxidizing agent solution at the irradiated site front end of irradiation reaction device.
Wherein, this nozzle system preferably is located on the radiation reactor of radioreaction system, is called second nozzle system.
The distance of this second nozzle system and irradiated site is preferably 1.5-4.5 rice.
The nozzle system of above-mentioned ejection oxidizing agent solution is the atomizer system preferably, can make the oxidizing agent solution particle diameter of ejection as far as possible little.
Positive progressive effect of the present invention is:
The present invention adds oxidizing agent solution before flue gas enters irradiated site, the one because solution in strong oxidizer can with sulfur dioxide (SO
2) and nitrogen oxide (NO
x) producing oxidation reaction improving desulfurization off sulfide effect, main cause is a flue gas when being subjected to electron beam irradiation, when producing a large amount of oxyradicals, also can produce a large amount of aqueous electron (e
- Aq) and reduction such as hydroperoxyl radical (H) free radical, the effect of these radical pair desulphurization denitrations is very little, and when spraying into oxidizing agent solution in the flue gas, these oxidants can react with aqueous electron and hydroperoxyl radical etc., thereby produce the OH hydroxyl radical free radical, and hydroxyl radical free radical is oxidation SO
2And NO
xMain strong oxidative free radical, thereby effectively improve denitrification efficiency.With the hydrogen peroxide is example, and the reaction of hydrogen peroxide and aqueous electron and hydroperoxyl radical is as follows:
As seen, the present invention is on the basis that keeps the prior art advantage, make the power demand of electron accelerator system obtain bigger reduction, improved the capacity usage ratio of electron beam, the construction costs of desulfurizing and denitrifying flue gas by electron beam device and power consumption all have improvement preferably, general power as the electron accelerator system is constant, and sulfur dioxide and removal efficiency of nitrogen oxides can effectively improve; Constant as sulfur dioxide and removal efficiency of nitrogen oxides, then the construction investment of electron accelerator system and power consumption can obtain bigger reduction.In addition, the inventive method is owing to having strengthened desulphurization reaction than prior art, so the chilling temperature of flue gas suitably can be improved with further reinforcement denitration reaction.
Description of drawings
Fig. 1 is the structural representation of existing desulfurizing and denitrifying flue gas by electron beam device;
Fig. 2 is the structural representation of the desulfurizing and denitrifying flue gas by electron beam device of one embodiment of the invention;
Fig. 3 is the local enlarged diagram of the radioreaction system in one embodiment of the invention.
The specific embodiment
Below in conjunction with drawings and Examples, the technological process of the inventive method and the structure composition of device thereof are described better, and effect of the present invention.
Embodiment 1
Referring to Fig. 2,3, device of the present invention mainly is to have increased atomizer 13 (U.S. BETE company) in the radioreaction system 78 of existing apparatus, and this nozzle 13 is located at radiation area 81 front ends of radiation reactor 8, and both differ 2m.
Implementing flow process of the present invention by it is: boiler 1 produced 500,000Nm
3The flue gas of/h (flue-gas temperature is 150 ℃) is incorporated into flue gas pretreater 4 through flue 2, in flue gas pretreater 4, cooling water sprays in the flue gas by nozzle system 3, and flue-gas temperature drops to about 75 ℃, and the flue gas behind the decreasing temperature and increasing humidity enters irradiation reaction device 8 through flue 6.In flue 6, spray into ammonia by pipeline 5, the same prior art of the straying quatity of ammonia, concentration and exhaust gas volumn according to sulfur dioxide and nitrogen oxide calculate by certain chemical equivalent, the atomizer 13 of flue gas through being located at irradiation reaction device front end that mixes ammonia sprays into hydrogenperoxide steam generator, the mass ratio of hydrogen peroxide and water is 1: 400 in the solution, the straying quatity of hydrogenperoxide steam generator is 2000kg/h, and the particle size range of the solution droplets that atomizer sprayed into is 30-50 μ m.Spray into mixed flue gas behind the oxidizing agent solution through the electron beam irradiation district, electron accelerator system 7 is installed in the irradiated site top, flue gas carries out the reaction that removes of sulfur dioxide and nitrogen oxide in irradiated site, and generation ammonium sulfate and ammonium nitrate product, these products and flue gas enter accessory substance through flue 9 together and collect device 10, in accessory substance gatherer 10, ammonium sulfate and ammonium nitrate product are collected, and the clean flue gas after the processing enters atmosphere by chimney 12 behind flue 11.
The dosage of present embodiment electron beam can drop to 3.5kGy, and at this moment the electron beam beam power has dropped to 630kW, when the general power of electron accelerator system drops to 740kW, and the removing index and can reach 90% and 50% respectively of sulfur dioxide and nitrogen oxide; Implement as pressing prior art, then the dosage of electron beam needs just can reach about 5kGy, and the electron beam beam power needs 900kW at least so, and the general power of electron accelerator system then needs 1050kW.On construction costs, it is the electron accelerator system (Japanese NISSIN high pressure company) of 400kW that prior art needs 3 cover power, and present embodiment only to need 2 cover power be the electron accelerator system of 400kW; Analyze from operating cost, the general power of present embodiment electron accelerator system drops to 740kW from 1050kW, and the per hour power consumption of electron accelerator system saves about 30%.
When the dosage of the electron beam of setting present embodiment is 3kGy, at this moment according to prior art, the index that removes of sulfur dioxide and nitrogen oxide is respectively 82% and 20%, and the electron beam beam power is 540kW so, and the general power of electron accelerator system then needs 635kW; Keep the general power of electron accelerator system constant by above-mentioned prior art as present embodiment, then present embodiment sulfur dioxide and removal efficiency of nitrogen oxides can reach 93% and 52%.
Embodiment 2
Atomizer 13 in the present embodiment device is 3m with the distance in electron beam irradiation district, and is surplus with embodiment 1.This technological process sprays into potassium peroxide solution at irradiation reaction device front end through atomizer 13, the mass ratio of potassium peroxide and water is 1: 4000 in the solution, the straying quatity of potassium peroxide solution is 2000kg/h, and the average grain diameter of the solution droplets that atomizer sprayed into is 60 μ m, and is surplus with embodiment 1.
To be respectively 90% and 50% be example with the index that removes of sulfur dioxide and nitrogen oxide, as implementing by prior art, then the dosage of electron beam needs just can reach about 5kGy, and the electron beam beam power needs 900kW at least so, and the general power of electron accelerator system then needs 1050kW; In the present embodiment, the dosage of electron beam can drop to and still can reach the same index that removes below the 4.5kGy, and at this moment the electron beam beam power has dropped to 810kW, and the general power of electron accelerator system drops to below the 953kW.At this moment, the general power of electron accelerator system is original 90%.
Spray into sodium peroxide solution at irradiation reaction device front end through atomizer 13, the ratio of sodium peroxide and water is 1: 1500 in the solution, the straying quatity of sodium peroxide solution is 1000kg/h, the distance in atomizer and electron beam irradiation district is 2.5m, the average grain diameter of the solution droplets that atomizer sprayed into is 80 μ m, and is surplus with embodiment 1.
The dosage of setting the electron beam of present embodiment is 3kGy, and at this moment according to prior art, the index that removes of sulfur dioxide and nitrogen oxide is respectively 82% and 20%, and the electron beam beam power is 540kW so, and the general power of electron accelerator system then needs 635kW; Present embodiment is constant as the general power that keeps the electron accelerator system, and then sulfur dioxide and removal efficiency of nitrogen oxides can reach 89% and 36%.
Embodiment 4
Spray into ammonium persulfate solution at irradiation reaction device front end through atomizer 13, the mass ratio of ammonium persulfate and water is 1: 1600 in the solution, the straying quatity of ammonium persulfate solution is 3000kg/h, the distance in atomizer and electron beam irradiation district is 1.5m, the particle diameter of the solution droplets that atomizer sprayed into is 200 μ m, and is surplus with embodiment 1.
The dosage of setting the electron beam of present embodiment is 3kGy, and at this moment according to prior art, the index that removes of sulfur dioxide and nitrogen oxide is respectively 82% and 20%, and the electron beam beam power is 540kW so, and the general power of electron accelerator system then needs 635kW; And the general power of present embodiment such as electron accelerator system is constant, and then sulfur dioxide and removal efficiency of nitrogen oxides can reach 92% and 42%.
Boiler 1 produced 500,000Nm
3The flue gas of/h (flue-gas temperature is 150 ℃) is incorporated into flue gas pretreater 4 through flue 2, and in flue gas pretreater 4, cooling water system still sprays into 21t/h by former decreasing temperature and increasing humidity technology, and flue-gas temperature drops to 75 ℃.Hydrogenperoxide steam generator can be joined in the cooling water, then together by nozzle system 3 (the certain atomizer that also can establish through other, figure does not show) spray into flue gas, the mass ratio of hydrogen peroxide and water is 1: 1200 in the hydrogenperoxide steam generator, the addition of hydrogenperoxide steam generator is 2000kg/h, and the average grain diameter of the solution droplets that atomizer sprayed into is 150 μ m.At this moment flue-gas temperature drops to about 68 ℃, behind the decreasing temperature and increasing humidity and the flue gas that adds hydrogenperoxide steam generator enter irradiation reaction device 8 through flue 6.In flue 6, spray into gas ammonia by pipeline 5.Mixed flue gas enters the irradiation reaction device and carries out electron beam irradiation, flue gas carries out the reaction that removes of sulfur dioxide and nitrogen oxide in irradiated site, and generation ammonium sulfate and ammonium nitrate product, these products and flue gas enter accessory substance through flue 9 together and collect device 10, in accessory substance gatherer 10, ammonium sulfate and ammonium nitrate product are collected, and the clean flue gas after the processing enters atmosphere by chimney 12 behind flue 11.
The dosage of setting the electron beam of present embodiment is 3kGy, and at this moment according to prior art, the index that removes of sulfur dioxide and nitrogen oxide is respectively 82% and 20%, and the electron beam beam power is 540kW so, and the general power of electron accelerator system then needs 635kW; The general power of present embodiment such as electron accelerator system is constant, and then sulfur dioxide and removal efficiency of nitrogen oxides can reach 88% and 28%.
Cooling water drops to flue-gas temperature about 95 ℃, spray into sodium peroxydisulfate solution at irradiation reaction device front end through atomizer 13, the mass ratio of sodium peroxydisulfate and water is 1: 50 in the solution, the straying quatity of sodium peroxydisulfate solution is 9000kg/h, the distance in atomizer and electron beam irradiation district is 4.5m, the average grain diameter of the solution droplets that atomizer sprayed into is 20 μ m, and is surplus with embodiment 1.
The dosage of setting the electron beam of present embodiment is 3kGy, and at this moment according to prior art, the index that removes of sulfur dioxide and nitrogen oxide is respectively 82% and 20%, and the electron beam beam power is 540kW so, and the general power of electron accelerator system then needs 635kW; The general power of present embodiment such as electron accelerator system is constant, and then sulfur dioxide and removal efficiency of nitrogen oxides can reach 93% and 56%.
Reagent in the foregoing description all is conventional commercial reagent.
As can be seen from the above-described embodiment, apparatus of the present invention can also be provided with nozzle system in other zone before the irradiated site of radiation reactor, as in flue 6; Also more than one nozzle system can be installed simultaneously on demand.And according to principle of the present invention, the oxidant in its method can also be potassium peroxydisulfate and other oxidants, as other peroxide etc.; As for its concentration of aqueous solution and aqueous solution quality and flue gas volume ratio, be that the big more then reaction of concentration dense more (being that oxidant is bigger than more with water quality), aqueous solution quality and flue gas volume ratio is better routinely, but should take all factors into consideration with regard to aspects such as its costs; In addition, this oxidizing agent solution also can be respectively from being divided into the nozzle system ejection of different parts; These all are that those skilled in the art can push away it according to convention, do not give unnecessary details one by one at this.
Claims (10)
1, a kind of method of desulfurizing and denitrifying flue gas by electron beam, it comprises the following steps:
1) the flue gas cooling damping that contains sulfur dioxide, nitrogen oxide that boiler is produced;
2) adding ammonia mixes with flue gas;
3) mixed flue gas is carried out electron beam irradiation and react, thereby make sulfur in smoke, nitrogen oxide generate ammonium sulfate and ammonium nitrate and be removed, realized gas cleaning;
It is characterized in that this method before the reaction of the electron beam irradiation of step 3), in flue gas, spray into oxidizing agent solution.
2, method according to claim 1 is characterized in that this oxidant is a peroxide.
3, method according to claim 2 is characterized in that this peroxide is selected from one or more in hydrogen peroxide, sodium peroxide, potassium peroxide, ammonium persulfate, sodium peroxydisulfate and the potassium peroxydisulfate.
4, method according to claim 1 is characterized in that this flue gas volume and the oxidizing agent solution mass ratio that is sprayed into are 10000Nm
3: 20-180kg, the mass ratio of oxidant and water is 1 in this oxidizing agent solution: 50-4000.
5, method according to claim 1, the size droplet diameter that it is characterized in that the oxidizing agent solution that sprayed into is below 200 μ m.
6, according to each described method of claim 1-5, it is characterized in that described in flue gas, spray into oxidizing agent solution be meant with the mixed flue gas of ammonia in spray into.
7, a kind of device of desulfurizing and denitrifying flue gas by electron beam, it includes first flue that links to each other with boiler; The flue gas pretreater that links to each other with this flue is equipped with first nozzle system that damping water is cooled off in ejection on this flue gas pretreater; One end and second flue that this flue gas pretreater links to each other which is provided with the pipeline that sprays ammonia; The irradiation reaction system that is connected with the other end of this second flue, this irradiation reaction system includes electron accelerator system and the irradiation reaction device that produces electron beam and carry out the electron beam irradiation reaction, and this electron accelerator system is installed on the irradiated site top of irradiation reaction device; It is characterized in that this device is provided with the nozzle system that at least one is used to spray oxidizing agent solution at the irradiated site front end of irradiation reaction device.
8, device according to claim 7 is characterized in that this nozzle system that is used to spray oxidizing agent solution is located at the irradiation reaction device of irradiation reaction system, is called second nozzle system.
9, device according to claim 8, the distance that it is characterized in that this second nozzle system and irradiated site is a 1.5-4.5 rice.
10, according to claim 7,8 or 9 described devices, the nozzle system that it is characterized in that this ejection oxidizing agent solution is the atomizer system.
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| 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 |
| CN102166467A (en) * | 2011-03-08 | 2011-08-31 | 张光太 | Method for synchronously separating CO2, SO2 and NOX from flue gas of coal-fired boiler by using electron beams |
| CN104258702A (en) * | 2014-10-16 | 2015-01-07 | 厦门大学 | Flue gas desulfurization and denitration method and device through electron beams |
| CN105854568A (en) * | 2016-06-07 | 2016-08-17 | 南京蓝色天空环保科技有限公司 | Low-temperature denitration flue reaction chamber |
| CN106989407A (en) * | 2016-01-20 | 2017-07-28 | 杭州中兵环保股份有限公司 | NOx cancellation elements and method in a kind of flue gas |
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| CN112657325A (en) * | 2019-10-15 | 2021-04-16 | 中国石油化工股份有限公司 | Method for removing nitrogen oxides from gas |
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| JP2001239131A (en) * | 2000-02-29 | 2001-09-04 | Mamoru Nakasuji | Desulfurization/denitration equipment and boiler equipment |
| CN1175918C (en) * | 2000-07-11 | 2004-11-17 | 清华大学 | Semi-dry fume-purifying linear pulse electron beam method |
| CN2616279Y (en) * | 2003-09-29 | 2004-05-19 | 四川恒泰环境技术有限责任公司 | Electronic beam ammonia flue gas desulfurizing and denitrating apparatus |
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- 2005-04-15 CN CNB2005100251316A patent/CN100361732C/en not_active Expired - Fee Related
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| CN102166467A (en) * | 2011-03-08 | 2011-08-31 | 张光太 | Method for synchronously separating CO2, SO2 and NOX from flue gas of coal-fired boiler by using electron beams |
| CN104258702A (en) * | 2014-10-16 | 2015-01-07 | 厦门大学 | Flue gas desulfurization and denitration method and device through electron beams |
| CN104258702B (en) * | 2014-10-16 | 2016-02-17 | 厦门大学 | A kind of method of desulfurizing and denitrifying flue gas by electron beam and device |
| CN106989407A (en) * | 2016-01-20 | 2017-07-28 | 杭州中兵环保股份有限公司 | NOx cancellation elements and method in a kind of flue gas |
| CN105854568A (en) * | 2016-06-07 | 2016-08-17 | 南京蓝色天空环保科技有限公司 | Low-temperature denitration flue reaction chamber |
| CN105854568B (en) * | 2016-06-07 | 2018-05-04 | 南京蓝色天空环保科技有限公司 | Low-temperature denitration flue reative cell |
| CN112657325A (en) * | 2019-10-15 | 2021-04-16 | 中国石油化工股份有限公司 | Method for removing nitrogen oxides from gas |
| CN111495158A (en) * | 2020-05-29 | 2020-08-07 | 广东佳德环保科技有限公司 | System and method for desulfurization and denitrification by cooperation of electron beam and oxidant |
| CN111495158B (en) * | 2020-05-29 | 2024-02-27 | 广东佳德环保科技有限公司 | System and method for desulfurizing and denitrating by electron beam cooperated with oxidant |
| CN112370952A (en) * | 2020-09-16 | 2021-02-19 | 江苏汇能环境工程有限公司 | Factory-used waste gas desulfurization and denitrification treatment device |
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