CN104474858A - Flue gas desulfurization and denitrification method and device and application of flue gas desulfurization and denitrification device - Google Patents
Flue gas desulfurization and denitrification method and device and application of flue gas desulfurization and denitrification device Download PDFInfo
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Abstract
The invention discloses a flue gas desulfurization and denitrification method comprising the following steps of carrying out heat exchange between flue gas generated by a boiler or a gas turbine and flue gas which is desulfurized and denitrified for the first time to cool the flue gas generated by the boiler; mixing the cooled flue gas and ammonia gas, and then, carrying out spray treatment with water; then, carrying out heat exchange between the flue gas which is desulfurized and denitrified for the first time and flue gas generated by the boiler to heat the flue gas which is desulfurized and denitrified for the first time; and simultaneously carrying out ultraviolet irradiation and electron beam irradiation on the heated flue gas which is desulfurized and denitrified for the first time. By using the method and a device disclosed by the invention, the heat of the flue gas can be effectively utilized to realize the sufficient heat exchange between two kinds of flue gas; and the optimal SOx and NOx removal temperatures are respectively reached in the two treatment processes, so that the desulfurization and denitrification efficiencies can be remarkably increased. The invention also discloses the device applying the method and application of the device.
Description
Technical field
The present invention relates to filed of flue gas purification, particularly a kind of method, device and uses thereof utilizing electron beam and UV treatment flue gas desulfurization and denitrification.
Background technology
Human health in the environmental pollution serious threat that atmosphere pollution brings.Wherein, the sulfur dioxide and the nitrogen oxide that comprise the large scale industry facilities exhaust such as thermal power plant, cement plant, garbage burning factory 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 engine, engine of boat and ship, gas turbine
xcontent is higher, reduces the NO in these combustion engine tail gas
xconcentration 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, and be difficult to natural degradation in the environment and eliminate, pole is insoluble in water, can be dissolved in majority of organic solvent, is the liposoluble substance of colorless and odorless, so be very easy to accumulate in vivo, serious to harm.Dioxin, except having carcinogenic toxicity, also has genotoxicity and genetoxic, directly endangers the Health and Living of descendants.Therefore dioxin contamination is the significant problem being 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 (SO
2) and nitrogen oxide (NO
x) etc. the flue gas of pollutant, by ionization and the excitation of electron beam, produce the free radical with strong oxidizing property.Simultaneously under the condition passing into ammonia and steam, these free radicals at a terrific speed with the SO in flue gas
2and NO
xreaction, generates the accessory substance that main component is ammonium sulfate and ammonium nitrate.By accessory substance collector and dust arrester removing accessory substance, the flue gas be 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 produced by coal-burning boiler 1 sends into flue gas pretreater 3 through the first flue 2, this flue gas pretreater 3 is provided with nozzle system 4, the suitable condition that cooling water makes flue gas cool-down be humidified to remove reaction can be sprayed, again flue gas is sent in the irradiation reaction device 7 of irradiation reaction system through the second flue 5, this irradiation reaction system is made up of irradiation reaction device 7 and Accelerating electron system 8, and certain stoichiometric ammonia is sprayed into 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 that Accelerating electron system 8 produces, after a series of chemical reaction, oxysulfide (SO in flue gas
2) and nitrogen oxide (NO
x) generate ammonium sulfate and ammonium nitrate, enter accessory substance collector 9 through flue together with the flue gas after process and collect these products by delivery pipe 10, and as fertilizer application, the flue gas after accessory substance collector 9 processes is entered in air by chimney 11.
There is following defect in above-mentioned prior art:
1) when the process of electron beam irradiation desulphurization denitration, in order to reach predetermined removal efficiency, the beam intensity of electron beam is needed to exceed certain threshold value.And electron beam can off-energy and beam intensity in the process penetrating flue gas.Therefore, in irradiation direction, the efficiency of fume treatment sharply reduces;
2) flue gas that coal-burning boiler produces must first through spray cooling, and heat is not utilized effectively; Further, desulfurization and denitration synchronously process in same reactor, cannot realize desulfurization and denitration and all be in best reaction and process conditions;
3) adopt in the process of conditional electronic bundle irradiation desulphurization denitration process, the dioxin produced in boiler smoke also fails effectively to be removed.
In view of this, the invention provides a kind of desulfurization denitration method and the 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 produced 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 engine produced carries out heat exchange with the flue gas of first time desulphurization denitration, makes flue gas cool-down;
2) by the flue gas mixing ammonia after cooling, then use Water spray process, complete first time desulphurization denitration;
3) flue gas that flue gas and boiler that first time departs from denitration produce is carried out heat exchange, make the flue gas intensification of described first time desulphurization denitration;
4) by heat up after first time desulphurization denitration flue gas carry out Ultraviolet radiation and electron beam irradiation simultaneously, complete second time desulphurization denitration.
In a preferred embodiment: the direction of described Ultraviolet radiation and the direction of described electron beam irradiation are relative direction.
In a preferred embodiment: described Ultraviolet radiation is two bundle ultraviolet relative exposures; Described electron beam irradiation is two beam electrons bundle relative lamp.
In a preferred embodiment: in step 2, the temperature of described Water spray process is 50-80 DEG C.
In a preferred embodiment: in step 3, described first time desulphurization denitration flue gas heat up after temperature be 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 of described Water spray process is atomizing spray.
In a preferred embodiment: described Water spray is the aqueous solution of 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 engine;
Fume treatment tower, described fume treatment tower is provided with spray system; 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 fume treatment tower, and described second flue is provided with spray ammonia control valve; The exhanst gas outlet of described fume treatment tower 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 and described ultraviolet generater are separately positioned on the relative sidewall locations of described reactor.
In a preferred embodiment: described electron accelerator is a pair, be separately positioned on the relative sidewall of described reactor.
In a preferred embodiment: described ultraviolet generater is a pair, the sidewall locations that described reactor is relative is separately positioned on.
In a preferred embodiment: the bottom angled of described irradiation reaction device, arranges byproduct discharge at the lowest part of reactor bottom.
In a preferred embodiment: described fume treatment tower bottom is provided with byproduct discharge.
In a preferred embodiment: between the exhanst gas outlet of described fume treatment tower and the pretreated fumes entrance of described flue gas-flue gas heat-exchange unit, be provided with the first accessory substance collector.
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 present invention also provides the device of described flue gas desulfurization and denitrification for the treatment of the purposes of boiler or combustion engine flue gas.This purposes may be used for removing SOx, the NOx in boiler smoke and dioxin comparatively up hill and dale.
The flue gas that boiler or combustion engine produce is carried out two step desulphurization denitration process respectively by fume treatment tower and irradiation reaction device by the present invention.First flue gas reduces temperature by flue gas-flue gas heat-exchange unit after boiler or combustion engine are discharged, then enters fume treatment tower after mixing with ammonia.The consumption of ammonia can draw according to stoichiometric amount.Water from the top spray of fume treatment tower, fully contact with the gaseous mixture of ammonia with flue gas, chemical reaction occur, carries out first time desulphurization denitration process.
The efficiency adopting the water smoke of the method for atomizing spray ejection and flue gas to contact with the gaseous mixture of ammonia is higher, because the size droplet diameter that spraying produces is less, reaction table area is larger, is more conducive to the generation of chemical reaction.SOx and NOx the water of ejection changed into the removal efficiency that hydrogen peroxide solution then significantly can promote first time desulphurization denitration process in above-mentioned spray process, this is because can be oxidized to H by hydrogen peroxide respectively
2sO
4and HNO
3, then be combined with ammonia and namely generate ammonium sulfate and ammonium nitrate, realize desulphurization denitration.
The temperature of flue gas after Water spray reaches 50-80 DEG C.Research mechanism according to relevant desulphurization reaction shows, desulphurization reaction mainly relies on thermal chemical reaction, and adopts electron beam irradiation to react less obvious to the action effect of desulphurization reaction.Desulphurization reaction principle is: the SOx in flue gas, O
2, H
2o and ammonia react generation ammonium sulfate.Experiment shows, when temperature is in 50-80 DEG C, 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 higher than 80 DEG C, the efficiency that SOx removes can significantly decline on the contrary along with the rising of temperature.In fume treatment tower, 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 fume treatment tower, can be used as Fertilizer application.Also containing a certain amount of dust in the component of flue gas, discharge again being deposited to fume treatment tower bottom after the effect of Water spray.Because dust can significantly affect removing of NOx in Subsequent electronic bundle denitration reaction, in fume treatment tower, therefore remove dust can play pretreated effect is carried out to electron beam denitration, and then the efficiency of remarkable lifting electron beam denitration reaction.
Discharge fume treatment tower together with the mist that the NOx be not yet removed and ammonia, steam and other smoke components form, and enter flue gas-flue gas heat-exchange unit by the 3rd flue.Mist, by entering irradiation reaction device again after heat exchanger raised temperature, carries out second step process, and under the irradiation of electron beam, remaining NOx and SOx is removed further.In second step process, N contained in flue gas
2, O
2, H
2o and CO
2deng gas molecule after electron beam irradiation, be converted into a large amount of OH, O, HO
2deng oxyradical, there is oxidation reaction and generate H in SOx and NOx in these free radicals and flue gas at a terrific speed
2sO
4and HNO
3(see document: Electron-beam flue-gas treatment for multicomponent air-pollution control, Applied Energy 75 (2003) 145154).The vaporific H produced
2sO
4and HNO
3with NH
3reaction generates sulfate of ammoniac and the ammonium nitrate of white powder.The research mechanism of relevant denitration reaction shows, in second step process, 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 NOx reaches best removal efficiency at such a temperature, is converted into ammonium nitrate more up hill and dale.
The present invention at the Main Function of second step process middle-ultraviolet lamp is: ultraviolet can by O
2and H
2o cracking generates OH free radical and O
3, thus the use amount of electron beam can be reduced, improve economy.The reaction mechanism of action of ultraviolet radiation is as follows:
H
2O+hν→H+·OH
O
2+hν→O(
1D)+O(
3P)
O (
1d)+M → O (
3p)+M (M=O
2or N
2)
O(
3P)+O
2+M→O
3+M
O
3+hν→O(
1D)+O
2
O(
1D)+H
2O→2·OH
It is not simple combination that technical scheme in the present invention utilizes ultraviolet and electron beam to carry out irradiation to mixed flue gas simultaneously.Electron beam and ultraviolet irradiation can produce the free radical of numerous species, comprise H, OH, H
2o
2, H
3o, HO
3, O
3deng.The effect of these free radicals in nitrogen oxides process is different, and the oxidation effectiveness of the radical pair sulfur dioxide that oxidisability is stronger and nitrogen oxide is better, more remarkable to the action effect of desulphurization denitration.Utilize ultraviolet and electron beam to carry out irradiation to mixed flue gas, its synergy is simultaneously: the H that electron beam can produce by ultraviolet
2o
2the OH useful to desulphurization denitration is further converted to Deng free radical.And the cost of ultraviolet irradiation device is well below electron accelerator, thus while guarantee desulfurization off sulfide effect, effectively reduce equipment cost and operating cost.
H
2o
2, free radical that the oxidisability such as OH is the strongest makes NOx, SO
2oxidized in the gas phase, change into solid-state ammonium nitrate and ammonium sulfate material.In irradiation reaction device, the reaction temperature of desulphurization denitration controls 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, thus reaches the technique effect simultaneously removing dioxin in flue gas.Except above-mentioned hydroxyl free radical, oxygen atom, ozone etc. produce except oxidation to dioxin, electron beam also can with dioxin molecule direct interaction, excited state molecule is become by Molecular Cloning for dioxin, when excited state molecule energy is greater than chemical bond energy, the fracture of chemical bond will be caused, the rearrangement of dioxin molecular structure or dislocation occur and is decomposed and removed.Ultraviolet irradiation then can produce significant facilitation to dioxin is Molecular Cloning for excited state.
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 reaches the best removal temperature of SOx and NOx respectively in above-mentioned two-step pretreatment process, can significantly improve the efficiency of desulfurization and denitration.In the process of first step fume treatment tower, a large amount of SOx and NOx is removed, NOx and the SOx treating capacity entered in second step irradiation reaction device is less, the power requirement of therefore required electron beam generating apparatus reduces, thus significantly can reduce investment and the operating cost of electron beam generating apparatus.Ultraviolet generater is comparatively cheap and easy to get.So increase the power requirement that ultraviolet generater can reduce electron beam generating apparatus further in second step irradiation reaction device, cost-saving.
In addition, the dioxin in irradiation reaction device under electron beam and ultraviolet double action in flue gas is also easily decomposed and removes.Method and apparatus of the present invention can be widely used in the process of various boiler (as: coal-burning boiler, garbage burning boiler, chemical industry incineration of waste boiler etc.) or combustion engine (as: diesel engine, gas turbine etc.) flue gas.
Accompanying drawing explanation
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 the relative position schematic diagram overlooking visual angle of electron accelerator in the irradiation reaction device of the embodiment of the present invention 1 and 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
See Fig. 2, flue gas is carried out two-step pretreatment respectively by fume treatment tower and irradiation reaction device by the present invention.The flue-gas temperature that boiler 1 produces is 130 DEG C, SO in flue gas
xcontent is 300ppm, NOx content is 200ppm.
The each assembly of desulfurizing and denitrifying flue gas by electron beam device shown in Fig. 2 and annexation 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;
Fume treatment tower 5, described fume treatment tower 5 is provided with spray system 6; The boiler flue gas outlet 32 of described flue gas-flue gas heat-exchange unit 3 is connected with the second flue 22 with the smoke inlet 51 of described fume treatment tower 5, and described second flue 22 is provided with spray ammonia control valve 4; The exhanst gas outlet 52 of fume treatment tower 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; Electron accelerator 8 installed by described irradiation reaction device 7.
First flue gas enters flue gas-flue gas heat-exchange unit 3 by the first flue 21 and reduces temperature after boiler 1 is discharged, then enters after the second flue 22 mixes with the ammonia controlling flow through spraying ammonia control valve 4 and enter fume treatment tower 5.The consumption of ammonia can draw according to stoichiometric amount.Make temperature in fume treatment tower 5 at 50 DEG C by controlling spray system 6; The atomizing effect of shower water is controlled by the nozzle bore controlling spray system 6.Shower water by spray system 6 from the top spray of fume treatment tower 5, fully contact with the gaseous mixture of ammonia with flue gas, chemical reaction occur, carries out the process of first step desulphurization denitration.
The efficiency adopting the water smoke of the method for atomizing spray ejection and flue gas to contact with the gaseous mixture of ammonia is higher, is more conducive to the generation of chemical reaction.SOx and NOx if change the water that spray system 6 sprays into hydrogen peroxide solution in above-mentioned spray process, significantly can promote the efficiency of first step desulphurization denitration process, this is because can be oxidized to H by hydrogen peroxide respectively
2sO
4and HNO
3, then be combined with ammonia and namely generate ammonium sulfate and ammonium nitrate.
Under the condition taking water as spray agent, the main purpose of first step desulphurization denitration process is the SOx removed in flue gas.In fume treatment tower 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 fume treatment tower, can be used as Fertilizer application.Discharge fume treatment tower 5 together with the mist that the NOx be not yet removed and ammonia, steam and other smoke components form, 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 raised temperature to 70 DEG C, carries out the process of second step desulphurization denitration.Under the irradiation of the electron beam of electron accelerator 8 generation, NOx and SOx generation chemical reaction is removed further.While electron beam irradiation, ultraviolet generater 71 (uviol lamp) produces Ultraviolet radiation flue gas, significantly promotes that NOx and SOx is converted into ammonium nitrate and ammonium sulfate through electron beam irradiation reaction.The dioxin contained in flue gas is also decomposed under electron beam and ultraviolet dual irradiation and removes 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.Flue gas after irradiation reaction device 7 processes is entered in air by chimney 11.
Electron accelerator 8 and ultraviolet generater 71 can be arranged on the inner wall position of irradiation reaction device 7, there is the permutation and combination method (as: horizontal direction irradiation and/or vertical direction irradiation) of 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 in horizontal direction and irradiate (as shown in Figure 3).Electron beam and ultraviolet overlapping region can be increased like this, be conducive to irradiation flue gas more fully.Setting electron-beam dose is 3kGy, and the ultraviolet wavelength that UV emitter produces is 300nm, and power is 20W, the removing index and can reach 94% and 79% respectively of sulfur dioxide and nitrogen oxide.If use hydrogen peroxide instead for spray agent in the process of first step desulphurization denitration, then the removing index and can be promoted to 96% and 83% respectively further of sulfur dioxide and nitrogen oxide.According to prior art, the index that removes of sulfur dioxide and nitrogen oxide is only 70% and 42% at identical conditions.
Embodiment 2
See Fig. 4, flue gas is carried out two-step pretreatment respectively by fume treatment tower and irradiation reaction device by the present invention.The flue-gas temperature that boiler 1 produces is 150 DEG C, and in flue gas, SOx content is 280ppm, NOx content is 200ppm.
The each assembly of flue gas desulfurization and denitrification device shown in Fig. 4 and annexation 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; Fume treatment tower 5, described fume treatment tower 5 is provided with spray system 6; 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 fume treatment tower 5, and described second flue 22 is provided with spray ammonia control valve 4; The exhanst gas outlet 52 of described fume treatment tower 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; Electron accelerator 8 installed by described irradiation reaction device 7.
First flue gas enters flue gas-flue gas heat-exchange unit 3 by the first flue 21 and reduces temperature after boiler 1 is discharged, then enters after the second flue 22 mixes with the ammonia controlling flow through spraying ammonia control valve 4 and enter fume treatment tower 5.The consumption of ammonia can draw according to stoichiometric amount.Make temperature in fume treatment tower 5 at 80 DEG C by controlling spray system 6; The atomizing effect of shower water is controlled by the nozzle bore controlling spray system 6.Shower water by spray system 6 from the top spray of fume treatment tower 5, fully contact with the gaseous mixture of ammonia with flue gas, chemical reaction occur, carries out the process of first step desulphurization denitration.
The contact surface area adopting the water smoke of the method for atomizing spray ejection and flue gas to contact with the gaseous mixture of ammonia is larger, is more conducive to the generation of chemical reaction.This step main purpose is the SOx removed in flue gas.In fume treatment tower 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 after fume treatment tower 5 processes 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.Discharge fume treatment tower 5 together with the mist that the NOx be not yet removed and ammonia, steam and other smoke components form, 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 raised temperature to 100 DEG C, carries out the process of second step desulphurization denitration, and under the irradiation of the electron beam produced at electron accelerator 8, NOx and SOx chemical reaction occurs is removed further.While electron beam irradiation, ultraviolet generater 73 (uviol lamp) produces Ultraviolet radiation flue gas, significantly promotes that NOx and SOx is converted into ammonium nitrate and ammonium sulfate through electron beam irradiation reaction.The dioxin contained in flue gas is also decomposed under electron beam and ultraviolet dual irradiation and removes in irradiation reaction device 7.
Second accessory substance collector 13 collects remaining byproduct of reaction ammonium nitrate and ammonium sulfate, and accessory substance can be used as Fertilizer application.Flue gas after accessory substance collector 13 processes is entered in air by chimney 11.
In the present embodiment, when to set electron-beam dose be 3kGy, the ultraviolet wavelength that UV emitter produces is 100nm, and power is 50W, the removing index and can reach 90% and 91% respectively of sulfur dioxide and nitrogen oxide.According to prior art, the index that removes of sulfur dioxide and nitrogen oxide is only 67% and 21% at identical conditions.
Embodiment 3
See Fig. 5, flue gas is carried out two-step pretreatment respectively by fume treatment tower and irradiation reaction device by the present invention.The flue-gas temperature that boiler 1 produces is 150 DEG C, and in flue gas, SOx content is 280ppm, NOx content is 200ppm.
Approximate in each assembly of flue gas desulfurization and denitrification device shown in Fig. 5 and annexation and embodiment 2, shown in specific 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; Fume treatment tower 5, described fume treatment tower 5 is provided with spray system 6; 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 fume treatment tower 5, and described second flue 22 is provided with spray ammonia control valve 4; The exhanst gas outlet 52 of described fume treatment tower 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; Electron accelerator 8 installed by described irradiation reaction device 7.
First flue gas enters flue gas-flue gas heat-exchange unit 3 by the first flue 21 and reduces temperature after boiler 1 is discharged, then enters after the second flue 22 mixes with the ammonia controlling flow through spraying ammonia control valve 4 and enter fume treatment tower 5.The consumption of ammonia can draw according to stoichiometric amount.Make temperature in fume treatment tower 5 at 80 DEG C by controlling spray system 6; The atomizing effect of shower water is controlled by the nozzle bore controlling spray system 6.Shower water by spray system 6 from the top spray of fume treatment tower 5, fully contact with the gaseous mixture of ammonia with flue gas, chemical reaction occur, carries out the process of first step desulphurization denitration.
The contact surface area that the present embodiment adopts the water smoke of the method for atomizing spray ejection and flue gas to contact with the gaseous mixture of ammonia is larger, is more conducive to the generation of chemical reaction.This step main purpose is the SOx removed in flue gas.In fume treatment tower 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 after fume treatment tower 5 processes 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.Discharge fume treatment tower 5 together with the mist that the NOx be not yet removed and ammonia, steam and other smoke components form, 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 raised temperature to 120 DEG C, carries out the process of second step desulphurization denitration.
In the present embodiment, in irradiation reaction device 7, realize electron beam and ultraviolet irradiation flue gas simultaneously.Ultraviolet radiation is two bundle ultraviolet relative exposures, and electron beam irradiation is two beam electrons bundle relative lamp.Therefore, ultraviolet generater is a pair, is separately positioned on the relative sidewall locations of irradiation reaction device 7 (only indicating a ultraviolet generater 73 in Fig. 5).Electron accelerator 81 and 82 is a pair, is separately positioned on the relative sidewall of irradiation reaction device 7.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 that the electron beam in irradiation reaction device and ultraviolet can be made to distribute more even, realize Electron Beam intensity of flow and the absorption energy of electron beam in flue gas realizes being uniformly distributed in the space of irradiation zone, effectively can avoid the region occurring being difficult to carry out fully reaction in irradiation reaction device.
Under the irradiation of the electron beam of electron accelerator 81 and 82 generation, NOx and SOx generation chemical reaction is removed further.While electron beam irradiation, ultraviolet generater 73 and 74 produces Ultraviolet radiation flue gas, significantly promotes that NOx and SOx is converted into ammonium nitrate and ammonium sulfate through electron beam irradiation reaction.The dioxin contained in flue gas is also decomposed under electron beam and ultraviolet dual irradiation and removes in irradiation reaction device 7.Owing to eliminating reaction dead angle, the removal efficiency of NOx, SOx and dioxin is all promoted.
Second accessory substance collector 13 collects remaining byproduct of reaction ammonium nitrate and ammonium sulfate, and accessory substance can be used as Fertilizer application.Flue gas after accessory substance collector 13 processes is entered in air by chimney 11.
In the present embodiment, when to set electron-beam dose be 3kGy, the ultraviolet wavelength that UV emitter produces is 400nm, and power is 40W, the removing index and can reach 91% and 93% respectively of sulfur dioxide and nitrogen oxide.According to prior art, the index that removes of sulfur dioxide and nitrogen oxide is only 67% and 21% at identical conditions.
Embodiment 4
See Fig. 7, large diesel engine flue gas peculiar to vessel is carried out two-step pretreatment respectively by fume treatment tower and irradiation reaction device by the present invention.The flue-gas temperature that large diesel engine peculiar to vessel produces is 350 DEG C, SO in flue gas
xcontent is 100ppm, NOx content is 200ppm.
The each assembly of desulfurizing and denitrifying flue gas by electron beam device shown in Fig. 7 and annexation 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;
Fume treatment tower 5, described fume treatment tower 5 is provided with spray system 6; The boiler flue gas outlet 32 of described flue gas-flue gas heat-exchange unit 3 is connected with the second flue 22 with the smoke inlet 51 of described fume treatment tower 5, and described second flue 22 is provided with spray ammonia control valve 4; The exhanst gas outlet 52 of fume treatment tower 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; Electron accelerator 8 installed by described irradiation reaction device 7.
First flue gas enters flue gas-flue gas heat-exchange unit 3 by the first flue 21 and reduces temperature after diesel engine 1 is discharged, then enters after the second flue 22 mixes with the ammonia controlling flow through spraying ammonia control valve 4 and enter fume treatment tower 5.The consumption of ammonia can draw according to stoichiometric amount.Make temperature in fume treatment tower 5 at 50 DEG C by controlling spray system 6; The atomizing effect of shower water is controlled by the nozzle bore controlling spray system 6.Shower water by spray system 6 from the top spray of fume treatment tower 5, fully contact with the gaseous mixture of ammonia with flue gas, chemical reaction occur, carries out the process of first step desulphurization denitration.
The efficiency adopting the water smoke of the method for atomizing spray ejection and flue gas to contact with the gaseous mixture of ammonia is higher, is more conducive to the generation of chemical reaction.SOx and NOx if change the water that spray system 6 sprays into hydrogen peroxide solution in above-mentioned spray process, significantly can promote the efficiency of first step desulphurization denitration process, this is because can be oxidized to H by hydrogen peroxide respectively
2sO
4and HNO
3, then be combined with ammonia and namely generate ammonium sulfate and ammonium nitrate.
Under the condition taking water as spray agent, the main purpose of first step desulphurization denitration process is the SOx removed in flue gas.In fume treatment tower 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 fume treatment tower, can be used as Fertilizer application.Discharge fume treatment tower 5 together with the mist that the NOx be not yet removed and ammonia, steam and other smoke components form, 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 raised temperature to 100 DEG C, carries out the process of second step desulphurization denitration.Under the irradiation of the electron beam of electron accelerator 8 generation, NOx and SOx generation chemical reaction is removed further.While electron beam irradiation, ultraviolet generater 71 (uviol lamp) produces Ultraviolet radiation flue gas, significantly promotes that NOx and SOx is converted into ammonium nitrate and ammonium sulfate through electron beam irradiation reaction.The dioxin contained in flue gas is also decomposed under electron beam and ultraviolet dual irradiation and removes 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.Flue gas after irradiation reaction device 7 processes is entered in air by chimney 11.
Electron accelerator 8 and ultraviolet generater 71 can be arranged on the inner wall position of irradiation reaction device 7, there is the permutation and combination method (as: horizontal direction irradiation and/or vertical direction irradiation) of 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 in horizontal direction and irradiate (as shown in Figure 3).Electron beam and ultraviolet overlapping region can be increased like this, be conducive to irradiation flue gas more fully.Setting electron-beam dose is 3kGy, and the ultraviolet wavelength that UV emitter produces is 300nm, and power is 20W, the removing index and can reach 94% and 87% respectively of sulfur dioxide and nitrogen oxide.If use hydrogen peroxide instead for spray agent in the process of first step desulphurization denitration, then the removing index and can be promoted to 96% and 93% respectively further of sulfur dioxide and nitrogen oxide.According to prior art, the index that removes of sulfur dioxide and nitrogen oxide is only 60% and 32% at identical conditions.
For purposes of illustration, foregoing description is given with reference to specific embodiment.But above-mentioned exemplary discussion is not want exhaustive to limit the invention to disclosed exact form.In view of above-mentioned instruction, many modifications and variations can be had.Selecting and describing these embodiments is to explain principle of the present invention and practical application thereof better, enables others skilled in the art utilize the present invention best thus and is suitable for each embodiment of conceived concrete purposes and various amendment.
Claims (21)
1. a method for flue gas desulfurization and denitrification, is characterized in that comprising the following steps:
1) flue gas boiler or combustion engine produced carries out heat exchange with the flue gas of first time desulphurization denitration, makes the flue gas cool-down that described boiler produces;
2) by the flue gas mixing ammonia after cooling, then use Water spray process, complete first time desulphurization denitration;
3) flue gas that flue gas and boiler that first time departs from denitration produce is carried out heat exchange, make the flue gas intensification of described first time desulphurization denitration;
4) by heat up after first time desulphurization denitration flue gas carry out Ultraviolet radiation and electron beam irradiation simultaneously, complete second time desulphurization denitration.
2. the method for a kind of flue gas desulfurization and denitrification according to claim 1, is characterized in that: the direction of described Ultraviolet radiation 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: described Ultraviolet radiation is two bundle ultraviolet relative exposures.
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 two beam electrons bundle relative lamp.
5. the method for flue gas desulfurization and denitrification as claimed in any of claims 1 to 4, is characterized in that: in step 2, and the temperature of described Water spray process is 50-80 DEG C.
6. the method for flue gas desulfurization and denitrification as claimed in any of claims 1 to 4, is characterized in that: in step 3, described first time desulphurization denitration flue gas heat up after temperature be 70-120 DEG C.
7. the method for flue gas desulfurization and denitrification as claimed in any of claims 1 to 4, is characterized in that: in step 4, and the temperature of described second time desulfurization and denitrification reaction is 70-120 DEG C.
8. the method for flue gas desulfurization and denitrification as claimed in any of claims 1 to 4, is characterized in that: in step 4, and described ultraviolet wavelength is 100-400nm.
9. the method for a kind of flue gas desulfurization and denitrification according to claim 5, is characterized in that: the mode of described Water spray process is atomizing spray.
10. the method for a kind of flue gas desulfurization and denitrification according to claim 9, is characterized in that: described Water spray is hydrogen peroxide spray.
The device of 11. 1 kinds of flue gas desulfurization and denitrifications, is characterized in that 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 engine;
Fume treatment tower, described fume treatment tower is provided with spray system; The exhanst gas outlet of described flue gas-flue gas heat-exchange unit is connected by the second flue with the smoke inlet of described fume treatment tower, and described second flue is provided with spray ammonia control valve; The exhanst gas outlet of described fume treatment tower connects the pretreated fumes entrance of described flue gas-flue gas heat-exchange unit by the 3rd flue;
Irradiation reaction device, this irradiation reaction device 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.
The device of 12. flue gas desulfurization and denitrifications according to claim 11, is characterized in that: described electron accelerator and described ultraviolet generater are separately positioned on the relative sidewall locations of described irradiation reaction device.
The device of 13. a kind of flue gas desulfurization and denitrifications according to claim 11, is characterized in that: described electron accelerator is a pair, is separately positioned on the relative sidewall of described irradiation reaction device.
The device of 14. a kind of flue gas desulfurization and denitrifications according to claim 11, is characterized in that: described ultraviolet generater is a pair, is separately positioned on the sidewall locations that described irradiation reaction device is relative.
15., according to claim 11 to the device of the flue gas desulfurization and denitrification in 14 described in any one, is characterized in that: described fume treatment tower bottom is provided with byproduct discharge.
16., according to claim 11 to the device of the flue gas desulfurization and denitrification in 14 described in any one, is characterized in that: the bottom angled of described irradiation reaction device, arranges byproduct discharge at the lowest part of reactor bottom.
17., according to claim 11 to the device of the flue gas desulfurization and denitrification in 14 described in any one, is characterized in that: be provided with the first accessory substance collector between the exhanst gas outlet of described fume treatment tower and the pretreated fumes entrance of described flue gas-flue gas heat-exchange unit.
18., according to claim 11 to the device of the flue gas desulfurization and denitrification in 14 described in any one, is characterized in that: the port of export of described irradiation reaction device connects the second accessory substance collector.
19., according to claim 11 to the device of the flue gas desulfurization and denitrification in 14 described in any one, is characterized in that: described spray system is atomizing sprinkling system.
The device of 20. a kind of flue gas desulfurization and denitrifications according to claim 19, is characterized in that: described spray system is the system of water injection system or spray hydrogen peroxide.
21. 1 kinds by the purposes of the device of the flue gas desulfurization and denitrification in claim 11 to 20 described in any one for the treatment of boiler or combustion engine flue gas.
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| CN105381699A (en) * | 2015-11-17 | 2016-03-09 | 东南大学 | Hydrogen peroxide oxidation combined amino wet desulphurization and denitration method and device |
| CN106178863A (en) * | 2016-08-16 | 2016-12-07 | 胡安平 | A kind of desulfurization denitration method of boiler smoke |
| CN107311117A (en) * | 2017-06-20 | 2017-11-03 | 中国石油集团东北炼化工程有限公司葫芦岛设计院 | Sulphur recovery and alkylation spent acid Combined Treatment process for cleanly preparing and device |
| 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 |
| 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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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105381699A (en) * | 2015-11-17 | 2016-03-09 | 东南大学 | Hydrogen peroxide oxidation combined amino wet desulphurization and denitration method and device |
| CN105381699B (en) * | 2015-11-17 | 2017-11-17 | 东南大学 | A kind of hydrogen peroxide oxidation joint amino wet desulphurization method of denitration and its device |
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| CN107311117A (en) * | 2017-06-20 | 2017-11-03 | 中国石油集团东北炼化工程有限公司葫芦岛设计院 | Sulphur recovery and alkylation spent acid Combined Treatment process for cleanly preparing and device |
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| 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 |
| 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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