CN104474858B - A kind of method of flue gas desulfurization and denitrification, device and uses thereof - Google Patents
A kind of method of flue gas desulfurization and denitrification, device and uses thereof Download PDFInfo
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- CN104474858B CN104474858B CN201410743754.6A CN201410743754A CN104474858B CN 104474858 B CN104474858 B CN 104474858B CN 201410743754 A CN201410743754 A CN 201410743754A CN 104474858 B CN104474858 B CN 104474858B
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Abstract
The invention discloses a kind of method of flue gas desulfurization and denitrification, comprise the following steps: that flue gas that boiler or combustion machine are produced and the flue gas of desulphurization denitration for the first time carry out heat exchange, the flue gas cool-down that described boiler is produced; By the flue gas mixing ammonia after cooling, then water spray is processed; Carry out heat exchange by departing from for the first time the flue gas that the flue gas of denitration and boiler produce again, described in making, the flue gas of desulphurization denitration heats up for the first time; The flue gas of the desulphurization denitration for the first time after heating up is carried out to ultraviolet ray simultaneously to be irradiated and electron beam irradiation. Method and apparatus of the present invention can effectively utilize flue gas heat, carries out the abundant heat exchange of flue gas-flue gas, and the best that reaches respectively SOx and NOx in two above-mentioned step processing procedures removes temperature, can significantly improve the efficiency of desulfurization and denitration. The invention also discloses device of application said method and uses thereof.
Description
Technical field
The present invention relates to filed of flue gas purification, particularly a kind of method of utilizing electron beam and UV treatment flue gas desulfurization and denitrification, device and uses thereof.
Background technology
Human health in the environmental pollution serious threat that atmosphere pollution brings. Wherein, comprise that sulfur dioxide and nitrogen oxide that the large scale industry facilities such as thermal power plant, cement plant, garbage burning factory discharge are one of main sources causing atmosphere pollution. Therefore, the flue gas desulfurization and denitrification problem of factory is the important process of thing of curbing environmental pollution at present. NO in the tail gas such as various large-scale diesel engines, engine of boat and ship, gas turbinexContent is higher, reduces the NO in these combustion tail gasxConcentration is also the focus that people pay close attention to all the time. In addition, thermal power plant, cement plant, garbage burning factory etc. also give off a large amount of dioxin, and the degree of concern that the dioxin that especially burning city domestic garbage produces is subject to is the highest. Dioxin is highly stable, is difficult to natural degradation and eliminates in environment, and the utmost point is insoluble in water, can be dissolved in majority of organic solvent, is the liposoluble substance of colorless and odorless, thus be very easy to accumulation in vivo, serious to harm. Dioxin, except having carcinogenic toxicity, also has genotoxicity and genetoxic, directly endangers descendants's Health and Living. Therefore dioxin contamination is the significant problem that is related to mankind's living or death, must strictly be controlled.
The technology of electron beam irradiation desulphurization denitration is the purifying coal-fired flue gas technology that development in recent years is got up, and this technology has entered the commercial Application stage at present. This technology utilizes high-energy electron beam irradiation to contain sulfur dioxide (SO2) and nitrogen oxide (NOx) etc. the flue gas of pollutant, by ionization and the excitation of electron beam, produce the free radical with strong oxidizing property. Passing under the condition of ammonia and steam simultaneously, these free radicals at a terrific speed with flue gas in SO2And NOXReaction, generating main component is the accessory substance of ammonium sulfate and ammonium nitrate. Remove accessory substance by accessory substance collector and dust arrester, the flue gas being purified.
Fig. 1 is the apparatus structure schematic diagram of existing electron beam irradiation flue gas desulfurization and denitrification. this electron beam irradiation flue gas desulfurization and denitration technique flow process is: the flue gas first coal-burning boiler 1 being produced is sent into flue gas pretreater 3 through the first flue 2, on this flue gas pretreater 3, nozzle system 4 is installed, can spray cooling water makes flue gas cool-down humidification to the suitable condition that removes reaction, again flue gas is sent into through the second flue 5 in the irradiation reaction device 7 of irradiation reaction system, this irradiation reaction system is made up of irradiation reaction device 7 and electronics accelerating system 8, and spray into certain stoichiometric ammonia by flow control valve 6 on the second flue 5, then mixed flue gas enters in irradiation reaction device 7 in the lump, under the electron beam irradiation effect producing in electronics accelerating system 8, after a series of chemical reaction, oxysulfide (SO in flue gas2) and nitrogen oxide (NOx) generate ammonium sulfate and ammonium nitrate, enter accessory substance collector 9 through flue together with flue gas after treatment and collect these products by delivery pipe 10, and as fertilizer application, enter in atmosphere by chimney 11 through accessory substance collector 9 flue gases after treatment.
There is following defect in above-mentioned prior art:
1), when the processing of electron beam irradiation desulphurization denitration, in order to reach predetermined removal efficiency, need the beam intensity of electron beam to exceed certain threshold value. And electron beam can off-energy and beam intensity in the process that penetrates flue gas. Therefore,, in irradiation direction, the efficiency of flue gas processing sharply reduces;
2) flue gas that coal-burning boiler produces must first pass through spray cooling, and heat is not utilized effectively; And desulfurization and denitration are synchronously processed in same reactor, cannot realize desulfurization and denitration all in best reaction and process conditions;
3) adopt in the process of conditional electronic bundle irradiation desulphurization denitration processing, the dioxin producing in boiler smoke also fails effectively to be removed.
In view of this, the invention provides a kind of desulfurization denitration method and device that can overcome above-mentioned defect.
Summary of the invention
In order to solve the problems referred to above and the defect of prior art, the invention provides a kind of method and device of flue gas desulfurization and denitrification, the method and device can significantly improve the utilization ratio of electron beam in desulphurization denitration process, reduce the operating cost of system for desulfuration and denitration, the dioxin simultaneously producing in boiler smoke also also can effectively be removed.
To achieve these goals, the invention provides a kind of method of desulfurizing and denitrifying flue gas by electron beam, comprise the following steps:
1) flue gas boiler or combustion machine being produced carries out heat exchange with the flue gas of desulphurization denitration for the first time, makes flue gas cool-down;
2) by the flue gas mixing ammonia after cooling, then the processing of water spray, desulphurization denitration for the first time completed;
3) carry out heat exchange by departing from for the first time the flue gas that the flue gas of denitration and boiler produce, described in making, the flue gas of desulphurization denitration heats up for the first time;
4) flue gas of the desulphurization denitration for the first time after heating up is carried out to ultraviolet ray simultaneously irradiate and electron beam irradiation, complete desulphurization denitration for the second time.
In a preferred embodiment: the direction that described ultraviolet ray is irradiated and the direction of described electron beam irradiation are relative direction.
In a preferred embodiment: it is two bundle ultraviolet ray relative exposures that described ultraviolet ray is irradiated; Described electron beam irradiation is the relative irradiation of two beam electrons bundles.
In a preferred embodiment: in step 2, the temperature that described water spray is processed is 50-80 DEG C.
In a preferred embodiment: in step 3, the temperature after the flue gas of described desulphurization denitration for the first time heats up is 70-120 DEG C.
In a preferred embodiment: in step 4, the temperature of described electron beam irradiation reaction is 70-120 DEG C.
In a preferred embodiment: in step 4, described ultraviolet wavelength is 100-400nm.
In a preferred embodiment: the mode that described water spray is processed is atomizing spray.
In a preferred embodiment: the aqueous solution that described water spray is spray hydrogen peroxide.
The present invention also provides a kind of device of desulfurizing and denitrifying flue gas by electron beam, comprising:
Flue gas-flue gas heat-exchange unit, the smoke inlet of described flue gas-flue gas heat-exchange unit is connected by the first flue with boiler or combustion machine;
Flue gas treating column, is provided with spray system on described flue gas treating column; The boiler flue gas outlet of described flue gas-flue gas heat-exchange unit is connected by the second flue with the smoke inlet of described flue gas treating column, and described the second flue is provided with spray ammonia control valve; The exhanst gas outlet of described flue gas treating column connects the pretreated fumes entrance of described flue gas-flue gas heat-exchange unit by the 3rd flue;
Reactor, this reactor is provided with electron accelerator and ultraviolet generater; The pretreated fumes outlet of described flue gas-flue gas heat-exchange unit connects described irradiation reaction device by the 4th flue.
In a preferred embodiment: described electron accelerator is separately positioned on described ultraviolet generater the sidewall locations that described reactor is relative.
In a preferred embodiment: described electron accelerator is a pair of, is separately positioned on the sidewall that described reactor is relative.
In a preferred embodiment: described ultraviolet generater is a pair of, is separately positioned on the sidewall locations that described reactor is relative.
In a preferred embodiment: the bottom angled of described irradiation reaction device, arranges accessory substance outlet at the lowest part of reactor bottom.
In a preferred embodiment: described flue gas treating column bottom is provided with accessory substance outlet.
In a preferred embodiment: be provided with the first accessory substance collector between the pretreated fumes entrance of the exhanst gas outlet of described flue gas treating column and described flue gas-flue gas heat-exchange unit.
In a preferred embodiment: the port of export of described irradiation reaction device connects the second accessory substance collector.
In a preferred embodiment: described spray system is atomizing sprinkling system.
In a preferred embodiment: described spray system is the system of water injection system or spray hydrogen peroxide.
The device of the flue gas desulfurization and denitrification described in the present invention also provides is for the treatment of the purposes of boiler or combustion engine flue gas. This purposes can be for removing SOx, NOx and the dioxin in boiler smoke comparatively up hill and dale.
The present invention carries out two step desulphurization denitration processing by flue gas treating column and irradiation reaction device respectively by the flue gas of boiler or the generation of combustion machine. First flue gas reduces temperature by flue gas-flue gas heat-exchange unit from boiler or the discharge of combustion machine, then after mixing with ammonia, enters flue gas treating column. The consumption of ammonia can draw according to stoichiometric amount. Water from the top spray of flue gas treating column and, fully contact with the gaseous mixture of flue gas and ammonia, there is chemical reaction, carry out desulphurization denitration processing for the first time.
The water smoke that adopts the method for atomizing spray to spray is higher with the efficiency that the gaseous mixture of flue gas and ammonia contacts, because the size droplet diameter that spraying produces is less, reaction table area is larger, is more conducive to the generation of chemical reaction. In above-mentioned spray process, the water of ejection is changed into hydrogen peroxide solution and can significantly promote the removal efficiency of desulphurization denitration processing for the first time, this is because hydrogen peroxide can be oxidized to H by SOx and NOx respectively2SO4And HNO3, then be combined and generate ammonium sulfate and ammonium nitrate with ammonia, realize desulphurization denitration.
The temperature of flue gas after water spray reaches 50-80 DEG C. Show according to the research mechanism of relevant desulphurization reaction, desulphurization reaction is mainly to rely on thermal chemical reaction, and adopts electron beam irradiation reaction less obvious to the action effect of desulphurization reaction. Desulphurization reaction principle is: the SOx in flue gas, O2，H2O and the ammonia generation ammonium sulfate that reacts. Experiment shows, in temperature during in 50-80 DEG C, and efficiency the best (reaching as high as 90%) that SOx removes, this step is mainly in order to remove the SOx in flue gas. When temperature is during higher than 80 DEG C, the efficiency that SOx removes is along with the rising of temperature can significantly decline on the contrary. In flue gas treating column, NOx also generates ammonium nitrate with oxygen, ammonia, water generation chemical reaction simultaneously, and therefore NOx also can be removed to a certain extent. Accessory substance ammonium sulfate and ammonium nitrate are discharged from the bottom of flue gas treating column, can be used as Fertilizer application. In the component of flue gas, also contain a certain amount of dust, after the effect spraying through water, be deposited to flue gas treating column bottom and discharge again. Due to significantly the removing of NOx in the follow-up electron beam denitration reaction of impact of dust, therefore in flue gas treating column, remove dust and can play electron beam denitration is carried out to pretreated effect, and then significantly promote the efficiency of electron beam denitration reaction.
Together with the mist that the NOx being not yet removed forms with ammonia, steam and other smoke components, discharge flue gas treating column, and enter flue gas-flue gas heat-exchange unit by the 3rd flue. Mist enters irradiation reaction device after by heat exchanger rising temperature again, carries out second step processing, and under the irradiation of electron beam, remaining NOx and SOx are further removed. In second step is processed, contained N in flue gas2、O2、H2O and CO2After electron beam irradiation, be converted into a large amount of OH Deng gas molecule, O, HO2Deng oxyradical, there is oxidation reaction and generate H in the SOx in these free radicals and flue gas and NOx at a terrific speed2SO4And HNO3(referring to document: Electron-beamflue-gastreatmentformulticomponentair-pollu tioncontrol, AppliedEnergy75 (2003) 145154). The vaporific H producing2SO4And HNO3With NH3Reaction generates sulfate of ammoniac and the ammonium nitrate of white powder. The research mechanism of relevant denitration reaction shows, in second step is processed, electron beam irradiation reaction is larger to the influencing factor of denitration reaction. Experiment shows, the mist temperature in irradiation reaction device is 70-120 DEG C, and at this temperature, NOx reaches best removal efficiency, is compared and is converted into up hill and dale ammonium nitrate.
The Main Function that the present invention processes middle-ultraviolet lamp at second step is: ultraviolet ray can be by O2And H2O cracking generates OH free radical and O3Thereby, can reduce the use amount of electron beam, improve economy. The reaction mechanism of action of ultraviolet radiation is as follows:
H2O+hν→H+·OH
O2+hν→O(1D)+O(3P)
O(1D)+M→O(3P)+M(M＝O2Or N2)
O(3P)+O2+M→O3+M
O3+hν→O(1D)+O2
O(1D)+H2O→2·OH
It is not simple combination that technical scheme utilization ultraviolet ray in the present invention is carried out irradiation to mixed flue gas with electron beam simultaneously. Electron beam and ultraviolet irradiation can produce the free radical of numerous species, comprise H, OH, H2O2、H3O、HO3、O3Deng. The effect of these free radicals in nitrogen oxide oxidizing process is different, and the radical pair sulfur dioxide that oxidisability is stronger and the oxidation effectiveness of nitrogen oxide are better, more remarkable to the action effect of desulphurization denitration. Utilize ultraviolet ray and electron beam mixed flue gas to be carried out to irradiation, its synergy is simultaneously: the H that ultraviolet ray can produce electron beam2O2Be further converted to the OH useful to desulphurization denitration Deng free radical. And the cost of ultraviolet irradiation device is well below electron accelerator, thereby in ensureing desulfurization off sulfide effect, effectively reduce equipment cost and operating cost.
H2O2, the strongest free radical of oxidisability such as OH makes NOx, SO2Oxidized in gas phase, change into solid-state ammonium nitrate and ammonium sulfate material. In irradiation reaction device, the reaction temperature of desulphurization denitration is controlled at 60-110 DEG C, and this temperature range can reach preferably SOx and NOx removal efficiency.
In above-mentioned mechanism, the dioxin in flue gas is oxidized decomposition under electron beam and ultraviolet double action also, thereby reaches the technique effect that simultaneously removes dioxin in flue gas. Except above-mentioned hydroxyl free radical, oxygen atom, ozone etc. produce oxidation dioxin, electron beam also can with dioxin molecule direct interaction, dioxin molecule is transformed into excited state molecule, in the time that excited state molecule energy is greater than chemical bond energy, will cause the fracture of chemical bond, the rearrangement of dioxin molecular structure or dislocation occur and be decomposed and remove. Ultraviolet irradiation can be converted into excited state to dioxin molecule and produce significant facilitation.
Beneficial effect of the present invention is:
Method and apparatus of the present invention can effectively utilize flue gas heat, carries out the abundant heat exchange of flue gas-flue gas, and the best that reaches respectively SOx and NOx in two above-mentioned step processing procedures removes temperature, can significantly improve the efficiency of desulfurization and denitration. In the processing of first step flue gas treating column, a large amount of SOx and NOx are removed, enter NOx and SOx treating capacity in second step irradiation reaction device less, therefore the power requirement of required electron beam generating apparatus reduces, thereby can significantly reduce investment and the operating cost of electron beam generating apparatus. Ultraviolet generater is comparatively cheap and easy to get. So in second step irradiation reaction device, increase ultraviolet generater and can further reduce the power requirement of electron beam generating apparatus, cost-saving.
In addition, in irradiation reaction device, under electron beam and ultraviolet double action, the dioxin in flue gas is also easily decomposed and removes. Method and apparatus of the present invention can be widely used in the processing of various boilers (as: coal-burning boiler, garbage burning boiler, chemical industry incineration of waste boiler etc.) or combustion machine (as: diesel engine, gas turbine etc.) flue gas.
Brief description of the drawings
Fig. 1 is the structural representation of the desulfurizing and denitrifying flue gas by electron beam device of prior art;
Fig. 2 is the structural representation of the flue gas desulfurization and denitrification device of the embodiment of the present invention 1;
Fig. 3 is electron accelerator in the irradiation reaction device of the embodiment of the present invention 1 and the relative position schematic diagram of overlooking visual angle of ultraviolet generater;
Fig. 4 is the structural representation of the flue gas desulfurization and denitrification device of the embodiment of the present invention 2;
Fig. 5 is the structural representation of the flue gas desulfurization and denitrification device of the embodiment of the present invention 3;
Fig. 6 is the electron accelerator at visual angle, irradiation reaction device longitudinal cross-section and the relative position schematic diagram of ultraviolet generater in the embodiment of the present invention 3;
Fig. 7 is the structural representation of the flue gas desulfurization and denitrification device of the embodiment of the present invention 4.
Detailed description of the invention
Embodiment 1
Referring to Fig. 2, the present invention carries out two step processing by flue gas treating column and irradiation reaction device respectively by flue gas. The flue-gas temperature that boiler 1 produces is 130 DEG C, SO in flue gasxContent is 300ppm, and NOx content is 200ppm.
The each assembly of desulfurizing and denitrifying flue gas by electron beam device and annexation shown in Fig. 2 is as follows:
The boiler smoke entrance 31 of flue gas-flue gas heat-exchange unit 3 is connected by the first flue 21 with boiler 1;
Flue gas treating column 5, is provided with spray system 6 on described flue gas treating column 5; The boiler flue gas outlet 32 of described flue gas-flue gas heat-exchange unit 3 is connected with the smoke inlet of described flue gas treating column 5 51 use the second flues 22, and described the second flue 22 is provided with spray ammonia control valve 4; The exhanst gas outlet 52 of flue gas treating column 5 connects the pretreated fumes entrance 33 of flue gas-flue gas heat-exchange unit 3 by the 3rd flue 23; The pretreated fumes outlet 34 of flue gas-flue gas heat-exchange unit 3 connects irradiation reaction device 7 by the 4th flue 24; On described irradiation reaction device 7, electron accelerator 8 is installed.
First flue gas enters flue gas-flue gas heat-exchange unit 3 by the first flue 21 and reduces temperature from boiler 1 is discharged, then enters the second flue 22 and enter flue gas treating column 5 through spraying after ammonia that ammonia control valve 4 controls flow mixes. The consumption of ammonia can draw according to stoichiometric amount. Make temperature in flue gas treating column 5 at 50 DEG C by controlling spray system 6; By controlling the atomizing effect of nozzle bore control shower water of spray system 6. Shower water by spray system 6 from the top spray of flue gas treating column 5 and, fully contact with the gaseous mixture of flue gas and ammonia, there is chemical reaction, carry out the processing of first step desulphurization denitration.
The water smoke that adopts the method for atomizing spray to spray is higher with the efficiency that the gaseous mixture of flue gas and ammonia contacts, and is more conducive to the generation of chemical reaction. Can significantly promote the efficiency of first step desulphurization denitration processing if the water in above-mentioned spray process, spray system 6 being sprayed changes hydrogen peroxide solution into, this is because hydrogen peroxide can be oxidized to H by SOx and NOx respectively2SO4And HNO3, then be combined with ammonia and generate ammonium sulfate and ammonium nitrate.
Taking water as spray agent condition under, the main purpose of first step desulphurization denitration processing is the SOx removing in flue gas. In flue gas treating column 5, NOx also generates ammonium nitrate with ammonia, water generation chemical reaction simultaneously, and therefore NOx also can be removed in large quantities. Accessory substance ammonium sulfate and ammonium nitrate are discharged from the bottom 9 of flue gas treating column, can be used as Fertilizer application. Together with the mist that the NOx being not yet removed forms with ammonia, steam and other smoke components, discharge flue gas treating column 5, and enter flue gas-flue gas heat-exchange unit 3 by the 3rd flue 23.
Mist enters irradiation reaction device 7 again by after flue gas-flue gas heat-exchange unit 3 rising temperature to 70 DEG C, carries out the processing of second step desulphurization denitration. Under the irradiation of the electron beam producing at electron accelerator 8, NOx and SOx generation chemical reaction are further removed. In electron beam irradiation, ultraviolet generater 71 (uviol lamp) produces ultraviolet ray and irradiates flue gas, significantly promotes NOx and SOx to be converted into ammonium nitrate and ammonium sulfate through electron beam irradiation reaction. The dioxin containing in flue gas is also decomposed and removes under electron beam and ultraviolet dual irradiation in irradiation reaction device 7.
Accessory substance ammonium nitrate and a small amount of ammonium sulfate are discharged from the bottom 10 of irradiation reaction device 7, and as fertilizer application. Enter in atmosphere by chimney 11 through irradiation reaction device 7 flue gases after treatment.
Electron accelerator 8 and ultraviolet generater 71 can be arranged on the inner wall position of irradiation reaction device 7, the permutation and combination method (as: horizontal direction irradiation and/or vertical direction irradiation) that has multiple position, all can produce certain irradiation effect to flue gas. In the present embodiment, the electron accelerator 8 in irradiation reaction device 7 and ultraviolet generater 71 are set to subtend irradiation (as shown in Figure 3) in horizontal direction. Can increase like this electron beam and ultraviolet overlapping region, be conducive to irradiation flue gas more fully. Setting electron-beam dose is 3kGy, and the ultraviolet wavelength that ultraviolet emission device produces is 300nm, and power is 20W, the removing index and can reach respectively 94% and 79% of sulfur dioxide and nitrogen oxide. If use hydrogen peroxide instead for spray agent in first step desulphurization denitration is processed, the removing index and can further be promoted to respectively 96% and 83% of sulfur dioxide and nitrogen oxide. According to prior art, under identical condition, the index that removes of sulfur dioxide and nitrogen oxide is only 70% and 42%.
Embodiment 2
Referring to Fig. 4, the present invention carries out two step processing by flue gas treating column and irradiation reaction device respectively by flue gas. The flue-gas temperature that boiler 1 produces is 150 DEG C, and in flue gas, SOx content is 280ppm, and NOx content is 200ppm.
The each assembly of flue gas desulfurization and denitrification device and annexation shown in Fig. 4 is as follows:
Flue gas-flue gas heat-exchange unit 3, the boiler smoke entrance 31 of described flue gas-flue gas heat-exchange unit 3 is connected by the first flue 21 with boiler 1; Flue gas treating column 5, is provided with spray system 6 on described flue gas treating column 5; The boiler flue gas outlet 32 of described flue gas-flue gas heat-exchange unit 3 is connected by the second flue 22 with the smoke inlet 51 of described flue gas treating column 5, and described the second flue 22 is provided with spray ammonia control valve 4; The exhanst gas outlet 52 of described flue gas treating column 5 connects the arrival end of the first accessory substance collector 12 by the 3rd flue 23, the port of export of the first accessory substance collector connects the pretreated fumes entrance 33 of flue gas-flue gas heat-exchange unit 3; The pretreated fumes outlet 34 of described flue gas-flue gas heat-exchange unit 3 connects the arrival end 71 of irradiation reaction device 7 by the 4th flue 24, the port of export 72 of described irradiation reaction device 7 connects the second accessory substance collector 13; On described irradiation reaction device 7, electron accelerator 8 is installed.
First flue gas enters flue gas-flue gas heat-exchange unit 3 by the first flue 21 and reduces temperature from boiler 1 is discharged, then enters the second flue 22 and enter flue gas treating column 5 through spraying after ammonia that ammonia control valve 4 controls flow mixes. The consumption of ammonia can draw according to stoichiometric amount. Make temperature in flue gas treating column 5 at 80 DEG C by controlling spray system 6; By controlling the atomizing effect of nozzle bore control shower water of spray system 6. Shower water by spray system 6 from the top spray of flue gas treating column 5 and, fully contact with the gaseous mixture of flue gas and ammonia, there is chemical reaction, carry out the processing of first step desulphurization denitration.
The water smoke that adopts the method for atomizing spray to spray is larger with the contact surface area that the gaseous mixture of flue gas and ammonia contacts, and is more conducive to the generation of chemical reaction. This step main purpose is the SOx removing in flue gas. In flue gas treating column 5, NOx also generates ammonium nitrate with ammonia, water generation chemical reaction simultaneously, and therefore NOx also can be removed in large quantities. Flue gas treating column 5 flue gas after treatment enters the first accessory substance collector 12 through the 4th flue 24 together and collects these accessory substances by delivery pipe 9, and accessory substance can be used as Fertilizer application. Together with the mist that the NOx being not yet removed forms with ammonia, steam and other smoke components, discharge flue gas treating column 5, and enter flue gas-flue gas heat-exchange unit 3 by the 3rd flue 23. Mist enters irradiation reaction device 7 again by after flue gas-flue gas heat-exchange unit 3 rising temperature to 100 DEG C, carries out the processing of second step desulphurization denitration, and under the irradiation of the electron beam producing at electron accelerator 8, NOx and SOx chemical reaction occurs are further removed. In electron beam irradiation, ultraviolet generater 73 (uviol lamp) produces ultraviolet ray and irradiates flue gas, significantly promotes NOx and SOx to be converted into ammonium nitrate and ammonium sulfate through electron beam irradiation reaction. The dioxin containing in flue gas is also decomposed and removes under electron beam and ultraviolet dual irradiation in irradiation reaction device 7.
The second accessory substance collector 13 is collected remaining byproduct of reaction ammonium nitrate and ammonium sulfate, and accessory substance can be used as Fertilizer application. Enter in atmosphere by chimney 11 through accessory substance collector 13 flue gases after treatment.
In the present embodiment, setting electron-beam dose while being 3kGy, the ultraviolet wavelength that ultraviolet emission device produces is 100nm, and power is 50W, the removing index and can reach respectively 90% and 91% of sulfur dioxide and nitrogen oxide. According to prior art, under identical condition, the index that removes of sulfur dioxide and nitrogen oxide is only 67% and 21%.
Embodiment 3
Referring to Fig. 5, the present invention carries out two step processing by flue gas treating column and irradiation reaction device respectively by flue gas. The flue-gas temperature that boiler 1 produces is 150 DEG C, and in flue gas, SOx content is 280ppm, and NOx content is 200ppm.
Approximate in the each assembly of flue gas desulfurization and denitrification device shown in Fig. 5 and annexation and embodiment 2, specific as follows shown in:
Flue gas-flue gas heat-exchange unit 3, the boiler smoke entrance 31 of described flue gas-flue gas heat-exchange unit 3 is connected by the first flue 21 with boiler 1; Flue gas treating column 5, is provided with spray system 6 on described flue gas treating column 5; The boiler flue gas outlet 32 of described flue gas-flue gas heat-exchange unit 3 is connected by the second flue 22 with the smoke inlet 51 of described flue gas treating column 5, and described the second flue 22 is provided with spray ammonia control valve 4; The exhanst gas outlet 52 of described flue gas treating column 5 connects the arrival end of the first accessory substance collector 12 by the 3rd flue 23, the port of export of the first accessory substance collector connects the pretreated fumes entrance 33 of flue gas-flue gas heat-exchange unit 3; The pretreated fumes outlet 34 of described flue gas-flue gas heat-exchange unit 3 connects the arrival end 71 of irradiation reaction device 7 by the 4th flue 24, the port of export 72 of described irradiation reaction device 7 connects the second accessory substance collector 13; Described irradiation reaction device 7 is installed electron accelerator 8.
First flue gas enters flue gas-flue gas heat-exchange unit 3 by the first flue 21 and reduces temperature from boiler 1 is discharged, then enters the second flue 22 and enter flue gas treating column 5 through spraying after ammonia that ammonia control valve 4 controls flow mixes. The consumption of ammonia can draw according to stoichiometric amount. Make temperature in flue gas treating column 5 at 80 DEG C by controlling spray system 6; By controlling the atomizing effect of nozzle bore control shower water of spray system 6. Shower water by spray system 6 from the top spray of flue gas treating column 5 and, fully contact with the gaseous mixture of flue gas and ammonia, there is chemical reaction, carry out the processing of first step desulphurization denitration.
The water smoke that the present embodiment adopts the method for atomizing spray to spray is larger with the contact surface area that the gaseous mixture of flue gas and ammonia contacts, and is more conducive to the generation of chemical reaction. This step main purpose is the SOx removing in flue gas. In flue gas treating column 5, NOx also generates ammonium nitrate with ammonia, water generation chemical reaction simultaneously, and therefore NOx also can be removed in large quantities. Flue gas treating column 5 flue gas after treatment enters the first accessory substance collector 12 through the 4th flue 24 together and collects these accessory substances by delivery pipe 9, and accessory substance can be used as Fertilizer application. Together with the mist that the NOx being not yet removed forms with ammonia, steam and other smoke components, discharge flue gas treating column 5, and enter flue gas-flue gas heat-exchange unit 3 by the 3rd flue 23. Mist enters irradiation reaction device 7 again by after flue gas-flue gas heat-exchange unit 3 rising temperature to 120 DEG C, carries out the processing of second step desulphurization denitration.
In the present embodiment, interior electron beam and the ultraviolet ray irradiation flue gas simultaneously realized of irradiation reaction device 7. It is two bundle ultraviolet ray relative exposures that ultraviolet ray is irradiated, and electron beam irradiation is the relative irradiation of two beam electrons bundles. Therefore, ultraviolet generater is a pair of, is separately positioned on the sidewall locations that irradiation reaction device 7 is relative (only indicating a ultraviolet generater 73 in Fig. 5). Electron accelerator 81 and 82 is a pair of, is separately positioned on the sidewall that irradiation reaction device 7 is relative. Fig. 6 is the longitudinal cross-section schematic diagram of irradiation reaction device 7, further indicates ultraviolet generater 73 and 74, and the relative position of electron accelerator 81 and 82. Adopt above-mentioned design can make electron beam and ultraviolet ray in irradiation reaction device distribute more even, realize Electron Beam intensity of flow and the electron beam absorption energy in flue gas and realize and being uniformly distributed in the space of irradiation zone, can effectively avoid in irradiation reaction device, occurring being difficult to carry out the fully region of reaction.
Under the irradiation of the electron beam producing at electron accelerator 81 and 82, NOx and SOx generation chemical reaction are further removed. In electron beam irradiation, ultraviolet generater 73 and 74 produces ultraviolet ray and irradiates flue gas, significantly promotes NOx and SOx to be converted into ammonium nitrate and ammonium sulfate through electron beam irradiation reaction. The dioxin containing in flue gas is also decomposed and removes under electron beam and ultraviolet dual irradiation in irradiation reaction device 7. Owing to having eliminated reaction dead angle, the removal efficiency of NOx, SOx and dioxin is all promoted.
The second accessory substance collector 13 is collected remaining byproduct of reaction ammonium nitrate and ammonium sulfate, and accessory substance can be used as Fertilizer application. Enter in atmosphere by chimney 11 through accessory substance collector 13 flue gases after treatment.
In the present embodiment, setting electron-beam dose while being 3kGy, the ultraviolet wavelength that ultraviolet emission device produces is 400nm, and power is 40W, the removing index and can reach respectively 91% and 93% of sulfur dioxide and nitrogen oxide. According to prior art, under identical condition, the index that removes of sulfur dioxide and nitrogen oxide is only 67% and 21%.
Embodiment 4
Referring to Fig. 7, the present invention carries out two step processing by flue gas treating column and irradiation reaction device respectively by large diesel engine flue gas peculiar to vessel. The flue-gas temperature that large diesel engine peculiar to vessel produces is 350 DEG C, SO in flue gasxContent is 100ppm, and NOx content is 200ppm.
The each assembly of desulfurizing and denitrifying flue gas by electron beam device and annexation shown in Fig. 7 is as follows:
The diesel engine smoke inlet 31 of flue gas-flue gas heat-exchange unit 3 is connected by the first flue 21 with diesel engine 1;
Flue gas treating column 5, is provided with spray system 6 on described flue gas treating column 5; The boiler flue gas outlet 32 of described flue gas-flue gas heat-exchange unit 3 is connected with the smoke inlet of described flue gas treating column 5 51 use the second flues 22, and described the second flue 22 is provided with spray ammonia control valve 4; The exhanst gas outlet 52 of flue gas treating column 5 connects the pretreated fumes entrance 33 of flue gas-flue gas heat-exchange unit 3 by the 3rd flue 23; The pretreated fumes outlet 34 of flue gas-flue gas heat-exchange unit 3 connects irradiation reaction device 7 by the 4th flue 24; On described irradiation reaction device 7, electron accelerator 8 is installed.
First flue gas enters flue gas-flue gas heat-exchange unit 3 by the first flue 21 and reduces temperature from diesel engine 1 is discharged, then enters the second flue 22 and enter flue gas treating column 5 through spraying after ammonia that ammonia control valve 4 controls flow mixes. The consumption of ammonia can draw according to stoichiometric amount. Make temperature in flue gas treating column 5 at 50 DEG C by controlling spray system 6; By controlling the atomizing effect of nozzle bore control shower water of spray system 6. Shower water by spray system 6 from the top spray of flue gas treating column 5 and, fully contact with the gaseous mixture of flue gas and ammonia, there is chemical reaction, carry out the processing of first step desulphurization denitration.
The water smoke that adopts the method for atomizing spray to spray is higher with the efficiency that the gaseous mixture of flue gas and ammonia contacts, and is more conducive to the generation of chemical reaction. Can significantly promote the efficiency of first step desulphurization denitration processing if the water in above-mentioned spray process, spray system 6 being sprayed changes hydrogen peroxide solution into, this is because hydrogen peroxide can be oxidized to H by SOx and NOx respectively2SO4And HNO3, then be combined with ammonia and generate ammonium sulfate and ammonium nitrate.
Taking water as spray agent condition under, the main purpose of first step desulphurization denitration processing is the SOx removing in flue gas. In flue gas treating column 5, NOx also generates ammonium nitrate with ammonia, water generation chemical reaction simultaneously, and therefore NOx also can be removed in large quantities. Accessory substance ammonium sulfate and ammonium nitrate are discharged from the bottom 9 of flue gas treating column, can be used as Fertilizer application. Together with the mist that the NOx being not yet removed forms with ammonia, steam and other smoke components, discharge flue gas treating column 5, and enter flue gas-flue gas heat-exchange unit 3 by the 3rd flue 23.
Mist enters irradiation reaction device 7 again by after flue gas-flue gas heat-exchange unit 3 rising temperature to 100 DEG C, carries out the processing of second step desulphurization denitration. Under the irradiation of the electron beam producing at electron accelerator 8, NOx and SOx generation chemical reaction are further removed. In electron beam irradiation, ultraviolet generater 71 (uviol lamp) produces ultraviolet ray and irradiates flue gas, significantly promotes NOx and SOx to be converted into ammonium nitrate and ammonium sulfate through electron beam irradiation reaction. The dioxin containing in flue gas is also decomposed and removes under electron beam and ultraviolet dual irradiation in irradiation reaction device 7.
Accessory substance ammonium nitrate and a small amount of ammonium sulfate are discharged from the bottom 10 of irradiation reaction device 7, and as fertilizer application. Enter in atmosphere by chimney 11 through irradiation reaction device 7 flue gases after treatment.
Electron accelerator 8 and ultraviolet generater 71 can be arranged on the inner wall position of irradiation reaction device 7, the permutation and combination method (as: horizontal direction irradiation and/or vertical direction irradiation) that has multiple position, all can produce certain irradiation effect to flue gas. In the present embodiment, the electron accelerator 8 in irradiation reaction device 7 and ultraviolet generater 71 are set to subtend irradiation (as shown in Figure 3) in horizontal direction. Can increase like this electron beam and ultraviolet overlapping region, be conducive to irradiation flue gas more fully. Setting electron-beam dose is 3kGy, and the ultraviolet wavelength that ultraviolet emission device produces is 300nm, and power is 20W, the removing index and can reach respectively 94% and 87% of sulfur dioxide and nitrogen oxide. If use hydrogen peroxide instead for spray agent in first step desulphurization denitration is processed, the removing index and can further be promoted to respectively 96% and 93% of sulfur dioxide and nitrogen oxide. According to prior art, under identical condition, the index that removes of sulfur dioxide and nitrogen oxide is only 60% and 32%.
For purposes of illustration, provided foregoing description with reference to specific embodiment. But above-mentioned exemplary discussion is not to want the exhaustive disclosed exact form that limits the invention to. In view of above-mentioned instruction, can there be many modifications and variations. Selecting and having described these embodiment is in order to explain better principle of the present invention and practical application thereof, makes thus others skilled in the art utilize best the present invention and is suitable for each embodiment and the various amendment of conceived concrete purposes.
Claims (18)
1. a method for flue gas desulfurization and denitrification, is characterized in that comprising the following steps:
1) flue gas boiler or combustion machine being produced carries out heat exchange with the flue gas of desulphurization denitration for the first time,The flue gas cool-down that described boiler is produced;
2) by the flue gas mixing ammonia after cooling, then the processing of water spray, desulfurization for the first time completed de-Nitre; The temperature that described water spray is processed is 50-80 DEG C;
3) carry out heat exchange by departing from for the first time the flue gas that the flue gas of denitration and boiler produce, described in makingThe flue gas of desulphurization denitration is warming up to 70-120 DEG C for the first time;
4) flue gas of the desulphurization denitration for the first time after heating up being carried out to ultraviolet ray simultaneously irradiates and electron beamIrradiation, completes desulphurization denitration for the second time; The temperature of described desulfurization and denitrification reaction is for the second time 70-120℃。
2. the method for a kind of flue gas desulfurization and denitrification according to claim 1, is characterized in that:The direction that described ultraviolet ray is irradiated and the direction of described electron beam irradiation are relative direction.
3. the method for a kind of flue gas desulfurization and denitrification according to claim 1, is characterized in that:It is two bundle ultraviolet ray relative exposures that described ultraviolet ray is irradiated.
4. the method for a kind of flue gas desulfurization and denitrification according to claim 1, is characterized in that:Described electron beam irradiation is the relative irradiation of two beam electrons bundles.
5. according to the method for the flue gas desulfurization and denitrification described in any one in claim 1 to 4, itsBe characterised in that: in step 4, described ultraviolet wavelength is 100-400nm.
6. the method for a kind of flue gas desulfurization and denitrification according to claim 1, is characterized in that:The mode that described water spray is processed is atomizing spray.
7. the method for a kind of flue gas desulfurization and denitrification according to claim 1, is characterized in that:Described water spray is hydrogen peroxide spray.
8. a device for flue gas desulfurization and denitrification, is characterized in that comprising:
Flue gas-flue gas heat-exchange unit, the smoke inlet of described flue gas-flue gas heat-exchange unit and boiler or combustion machine are logicalCrossing the first flue is connected;
Flue gas treating column, is provided with spray system on described flue gas treating column; Described flue gas-flue gas changesThe exhanst gas outlet of hot device is connected by the second flue with the smoke inlet of described flue gas treating column, and describedTwo flues are provided with spray ammonia control valve; The exhanst gas outlet of described flue gas treating column connects by the 3rd flueThe pretreated fumes entrance of described flue gas-flue gas heat-exchange unit;
Irradiation reaction device, this irradiation reaction device is provided with electron accelerator and ultraviolet generater; DescribedThe pretreated fumes outlet of flue gas-flue gas heat-exchange unit connects described irradiation reaction device by the 4th flue.
9. the device of flue gas desulfurization and denitrification according to claim 8, is characterized in that: described inElectron accelerator is separately positioned on the relative sidewall of described irradiation reaction device with described ultraviolet generaterPosition.
10. the device of a kind of flue gas desulfurization and denitrification according to claim 9, is characterized in that:Described electron accelerator is a pair of, is separately positioned on the sidewall that described irradiation reaction device is relative.
The device of 11. a kind of flue gas desulfurization and denitrifications according to claim 8, is characterized in that:Described ultraviolet generater is a pair of, is separately positioned on the relative sidewall locations of described irradiation reaction device.
The device of the flue gas desulfurization and denitrification in 12. according to Claim 8 to 11 described in any one,It is characterized in that: described flue gas treating column bottom is provided with accessory substance outlet.
The device of the flue gas desulfurization and denitrification in 13. according to Claim 8 to 11 described in any one,It is characterized in that: the bottom angled of described irradiation reaction device, arranges pair at the lowest part of reactor bottomProduct outlet.
The device of the flue gas desulfurization and denitrification in 14. according to Claim 8 to 11 described in any one,It is characterized in that: the pre-place of the exhanst gas outlet of described flue gas treating column and described flue gas-flue gas heat-exchange unitBetween reason smoke inlet, be provided with the first accessory substance collector.
The device of the flue gas desulfurization and denitrification in 15. according to Claim 8 to 11 described in any one,It is characterized in that: the port of export of described irradiation reaction device connects the second accessory substance collector.
The device of the flue gas desulfurization and denitrification in 16. according to Claim 8 to 11 described in any one,It is characterized in that: described spray system is atomizing sprinkling system.
The device of 17. a kind of flue gas desulfurization and denitrifications according to claim 16, is characterized in that:Described spray system is the system of water injection system or spray hydrogen peroxide.
18. 1 kinds by the device of the flue gas desulfurization and denitrification described in any one in claim 8 to 17For the treatment of the purposes of boiler or combustion engine flue gas.
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| CN106178863A (en) * | 2016-08-16 | 2016-12-07 | 胡安平 | A kind of desulfurization denitration method of boiler smoke |
| CN107311117B (en) * | 2017-06-20 | 2024-01-12 | 中国石油集团东北炼化工程有限公司葫芦岛设计院 | Clean production process and device for combined treatment of sulfur recovery and alkylated waste acid |
| CN109499326A (en) * | 2018-12-13 | 2019-03-22 | 江苏菲达环保科技有限公司 | A kind of method of flue gas desulfurization and denitrification |
| CN111075539A (en) * | 2019-12-31 | 2020-04-28 | 北京工业大学 | Method for desulfurization and denitrification of ship tail gas |
| CN112370952B (en) * | 2020-09-16 | 2022-11-08 | 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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