CN202096874U - Flue gas purification device based on advanced oxidization combined with wet washing - Google Patents
Flue gas purification device based on advanced oxidization combined with wet washing Download PDFInfo
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- CN202096874U CN202096874U CN2011200481075U CN201120048107U CN202096874U CN 202096874 U CN202096874 U CN 202096874U CN 2011200481075 U CN2011200481075 U CN 2011200481075U CN 201120048107 U CN201120048107 U CN 201120048107U CN 202096874 U CN202096874 U CN 202096874U
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- flue gas
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Abstract
A flue gas purification device based on advanced oxidization combined with wet washing is provided with a combustion and discharge system composed of a boiler, an ozone generator, a stirrer, a swirl nozzle, a reactor, a gas-liquid absorption tower and a chimney; flue gas including sulfur-containing oxides, nitric oxides and mercury generated by the boiler combustion, together with O3 generated by the ozone generator, enters the stirrer to be mixed, flows through the swirl nozzle and is sprayed into the reactor with an ultraviolet lamp tube; under the radiation excitation of ultraviolet light, hydroxyl radical (OH) with strong oxidizability is generated, and is oxidized to be gaseous products with higher dissolubility together with SO2 and indissoluble NO and Hg<0> in the flue gas; the gaseous products enter the gas-liquid absorption tower and are absorbed and desorbed by water; Hg<2+> generated in the gas-liquid absorption tower is used for collecting and recovering mercuric sulfide by addition of sulfidion S<2-> with the equal mole ratio; the remained sulfuric acid and nitric acid mixed solution serves as industrial raw materials to be recycled; and the washed flue gas enters the chimney to be discharged.
Description
Technical field
The utility model relates to the control of smoke emissioning pollution thing in the combustion process, relates in particular to a kind of smoke eliminator that combines wet scrubbing based on advanced oxidation.
Background technology
The oxysulfide that produces in the combustion process, nitrogen oxide and mercury can cause acid rain, photochemical fog and serious harms such as carcinogenic and teratogenesis.Therefore, researching and developing effective flue gas desulfurization and denitrification demercuration method is one of vital task of various countries' environmental protection scientific and technical personnel.In the last few years; Although people have developed a large amount of flue gas desulfurization and denitrification demercuration technology; But because human cognitive process's limitation and scientific technological advance is gradual; Existing various desulfurization denitration demercuration technology only was directed against single pollutant for removing target originally in research and development, removed when generally can't realize flue gas multiple pollutant.For example, use more flue gas desulfurization and denitrification technology at present and be mainly wet method limestone-gypsum method flue gas desulfurization technology (Ca-WFGD) and ammine selectivity catalytic reduction method (NH
3-SCR),, all can't in a reactor, realize removing simultaneously though these two kinds of technologies can be distinguished independent desulphurization denitration.Though the stack of uniting of two kinds of technologies is used and can be realized desulphurization denitration simultaneously, also causes whole system complicated simultaneously, floor space is big, investment and the high deficiency of operating cost.In addition, along with the mankind to the improving constantly of environmental requirement, also put into effect gradually to the laws and regulations of mercury emissions control in the flue gas, use but also there is a kind of cost-effective flue gas demercuration technology to obtain large-scale commercial applications at present.If at existing C a-WFGD and NH
3-SCR system for desulfuration and denitration afterbody increases independent flue gas demercuration system once more, then certainly will will cause the initial outlay of whole system and operating cost further sharply to increase, and finally is difficult in developing country's acquisition large-scale commercial applications and uses.
In sum, if can in a reactor, oxysulfide, nitrogen oxide and mercury realized removing simultaneously, then can reduce the complexity and the floor space of system greatly, and then reduce the initial cost and the operating cost of system.The wet type flue gas desulphurization technology is a kind of traditional flue gas treatment technology; Have that initial cost is little, technological process is simple and is easy to realize characteristics such as multi-pollutant removes simultaneously; It is the flue gases purification that a kind of extremely has the development and application prospect; But the progress of traditional wet flue gases purification is slow relatively always, and its main cause just is to contain respectively in nitrogen oxide and the mercury element NO of 90% above indissoluble and the Hg of 40-80% indissoluble
0Can know that by double-film theory gas molecule in space must at first dissolve in liquid phase by gaseous state through mass transfer and diffusion process, chemical reaction could take place then be fixed in the absorption liquid, and NO and Hg
0The characteristic of indissoluble makes its absorption resistance to mass tranfer in liquid phase increase greatly, only is difficult to significantly improve NO and Hg through regulation and control absorption liquid pH and method of temperature
0In the solubility of liquid phase, this characteristic has caused traditional wet desulfurization denitration demercuration technology ubiquity desulfuration efficiency high, but deficiency such as denitration and demercuration efficient is low, in fact can't realize desulfurization denitration demercuration real the time.Therefore, searching can be with NO and Hg
0Being converted into easy molten effective morphological fast is one of key that addresses this problem.
Summary of the invention
The utility model discloses a kind of smoke eliminator that combines wet scrubbing based on advanced oxidation; Utilize the ultraviolet excitation ozone decomposition to cause chain reaction; And produce hydroxyl radical free radical (OH) with strong oxidizing property; With oxysulfide, nitrogen oxide and the mercury oxidation of the reactor of flowing through is the gaseous products of highly dissoluble, and washing removes through the wet absorption system then, and then realizes the purpose of desulfurization denitration demercuration simultaneously.
For realizing above purpose; The embodiment that the utility model adopts is: a kind of smoke eliminator that combines wet scrubbing based on advanced oxidation; It is characterized in that: be provided with burning and exhaust system that boiler, ozone generator, agitator, swirl nozzle, reactor, Gas-Liquid Absorption tower and chimney constitute, the O that flue gas that comprises sulfur-containing oxide, nitrogen oxide and mercury that boiler combustion produces and ozone generator produce
3The swirl nozzle of flowing through after mixing in the common entering agitator sprays in the reactor that is provided with ultraviolet lamp tube, under ultraviolet radiation excites, produces the hydroxyl radical free radical (OH) of strong oxidizing property and the SO in the flue gas
2NO and Hg with indissoluble
0Be oxidized to the higher gaseous products of dissolubility and comprise SO
3, H
28O
4, NO
2, HNO
2, HNO
3, Hg (OH)
2And HgO, it is interior by the water absorbing and removing to get into the Gas-Liquid Absorption tower, the Hg that generates in the Gas-Liquid Absorption tower
2+Sulfidion S through mol ratios such as interpolations
2-Catch the recovery mercuric sulphide, remaining sulfuric acid and nitric acid mixed solution are recycled as the raw material of industry, and the flue gas after the washing gets into smoke stack emission.
Said O
3Dosage be 50ppm-1000ppm.
Said ultraviolet lamp tube is arranged on the Reactor inlet end, and it is consistent with the reactor import and export flow direction that ultraviolet lamp tube is provided with direction, and the effective ultraviolet radiation power of unit volume is 5W/m in the reactor
3-200W/m
3, the W/m of unit wherein
3Be meant reactor before uviol lamp is not installed, the needed ultraviolet radiation power of unit volume when reactor is void tower; The ultraviolet light EWL is 120nm-360nm.
When many ultraviolet lamp tubes were set, many ultraviolet lamp tubes were the concentric circles setting, and distance is identical between the neighboring concentric circle; Many ultraviolet lamp tubes are distributed on the circumference of different-diameter; Along same diameter line setting, the central angle between each adjacent two diameter line is identical, and circle centre position is provided with ultraviolet lamp tube; Swirl nozzle is arranged on the concentric circumference with ultraviolet lamp tube concentric circles alternate intervals and is uniformly distributed with, and places on the diameter line of ultraviolet lamp tube central angle half-angle, and the exit velocity of nozzle is at 5m/s-30m/s.
Sulfidion (the S that adds in the said Gas-Liquid Absorption tower
2-) mole should with Hg solution in the Gas-Liquid Absorption tower
2+Mole keep to equate i.e. n (S
2-): n (Hg
2+)=1: 1.
The course of reaction of this device:
1) ozone causes the reaction mechanism that chain reaction produces strong oxidizing property hydroxyl radical free radical (OH) under UV-irradiation:
O
3+hv→·O+O
2 (1)
·O+H
2O→2·OH (2)
2) SO
2, NO and Hg
0Be oxidized to and be prone to molten gaseous products SO
3, H
2SO
4, NO
2, HNO
2, HNO
3, Hg (OH)
2And HgO:
NO+·O→NO
2 (3)
NO+·OH→NO
2+·H (4)
NO+O
3→NO
2+O
2 (5)
NO+·OH→HNO
2 (6)
NO
2+·OH→HNO
3 (7)
HNO
2+·O→HNO
3 (8)
HNO
2+·OH→HNO
3+·H (9)
HNO
2+O
3→HNO
3+O
2 (10)
SO
2+·O→SO
3 (11)
SO
2+·OH→SO
3+·H (12)
SO
2+O
3→SO
3+O
2 (13)
SO
2+·OH→HSO
3 (14)
HSO
3+·OH→H
2SO
4 (15)
Hg
0+·OH→HgO+·H (16)
Hg
0+2·OH→Hg(OH)
2 (17)
Hg
0+O
3→HgO+O
2 (18)
3) the gaseous state Hg of highly dissoluble
2+By S
2+The HgS that solution absorption and reaction generate indissoluble, recycle through after the precipitate and separate then:
Hg
2++S
2-→HgS↓ (19)
4) after the heavy metal Hg element is recovered, the sulfuric acid and the nitric acid mixed solution that only are left high concentration in the solution can be used as raw material of industry recycling.
Advantage of the utility model and remarkable result: ozone can cause chain reaction and produce the hydroxyl radical free radical (OH) with strong oxidizing property under UV-irradiation, and the reaction rate constant of OH and most pollutants is up to 10
8-10
10Mol/Ls can attack multiple pollutant easily and it is degraded to harmless product.
(1) with the wet method limestone-gypsum method flue gas desulfurization technology (Ca-WFGD) and the ammine selectivity catalytic reduction method (NH that have obtained at present extensive use
3-SCR) compare; The utility model is desulfurization denitration demercuration simultaneously, is easy in a reactor, realize removing in the multiple pollutant in the flue gas, thereby can significantly reduces the complexity of system; The initial outlay of minimizing system and operating cost have very high exploitation and using value;
(2) compare with conventional wet oxidation technologies such as potassium permanganate, sodium chlorite and potassium peroxydisulfates, the hydroxyl radical free radical OH that the utility model produces is a kind of environment-friendly type strong oxidizer, the sulfuric acid of generation and salpeter solution and Hg
2+All can realize recycling, the entire reaction course non-secondary pollution, and conventional oxidation process such as potassium permanganate, sodium chlorite and potassium peroxydisulfate can produce complicated accessory substance, bring very big difficulty to post processing;
(3) with the applicant (a kind of system for desulfuration and denitration based on the photochemistry advanced oxidation time: 201012096592.5) with (a kind of flue gas demercuration system based on the effect of photochemistry advanced oxidation: 201012096592.8) compare, the utility model also has following many remarkable advantages and technical characterstic:
1) Along with people's improving constantly to environmental requirement; Laws and regulations to mercury emissions control in the flue gas are also put into effect gradually; The present invention can realize removing in three kinds of pollutants such as oxysulfide, nitrogen oxide and heavy metal element mercury in a reactor, thereby can further reduce the initial outlay and the operating cost of system.Along with the mankind to the improving constantly of environmental requirement, this advantage of the utility model will be highlighted gradually, and 201012096592.5 and 201012096592.8 all can't realize removing in three kinds of pollutants in same reactor;
2) the pollutant removing process of the utility model belongs to the homogeneous reaction process of dry method; Thereby chemical reaction process can not spread or the control of mass transfer link; And 201012096592.5 and 201012096592.8 are heterogeneous reaction processes of a wet method, because NO and Hg
0Solubility very low; The controlling unit of absorption process concentrates on gas-liquid mass transfer or diffusion process, thereby causes the resistance to mass tranfer of absorption process to increase greatly, and the utility model belongs to the homogeneous reaction process; Need not to consider the gas-liquid mass transfer resistance, course of reaction will be more efficiently favourable;
3) 201012096592.5 and 201012096592.8 described desulphurization denitrations or demercuration process all belong to the wet method subtractive process; Thereby uviol lamp need be immersed in the solution fully; But since the penetration capacity of uviol lamp in solution very a little less than, so the luminous energy effective rate of utilization is very low.In addition, because ultraviolet light is shorter at the penetration range of liquid phase, under the prerequisite that satisfies the same treatment amount; Need in the reactor to arrange more uviol lamp equipment, this will cause reactor volume to increase greatly, finally also increase initial cost and operating cost; And the utility model is the homogeneous reaction process of a dry method; Ultraviolet light is in air, to propagate, and the light penetration range will increase greatly, and the effective rate of utilization of luminous energy also will be significantly improved.Therefore, the utility model will have bigger technology and economic advantages;
4) 201012096592.5 and 201012096592.8 is subtractive process of a wet method, because reactant and product are in the same reactor, along with the carrying out of pollutant removing process, sulfate radical in the solution and nitrate concentration will increase gradually.This moment, the ion salting-out effect of solution will significantly increase, and finally can cause NO and Hg
0Solubility obviously descend.Thereby; Under the prerequisite that satisfies the pollutant removing index; In fact system will be difficult to unrestrictedly produce high-concentration sulfuric acid and the salpeter solution that can meet the need of market, and the cost that a large amount of nitric acid that course of reaction produces and sulfuric acid weak solution will increase after-treatment greatly.The oxidation reaction process of the utility model is a dry removal process; Oxidation product is all the gas-phase product of high-dissolvability; Afterbody independently absorption and washing system can fully absorb gas-phase product and not influence the operational effect of photochemical oxidation process itself; Thereby can produce the sulfuric acid and the salpeter solution of high concentration fully, reduce the after-treatment cost, this technological improvement has important techniques and economic worth undoubtedly in large-scale industrial application in the future.
The desulfurization denitration demercuration system had all shown bigger technology and economic advantages with respect to existing main flue gases purification, whole desulfurization denitration demercuration process non-secondary pollution when in sum, the utility model was described.Be of very high actual application value.
Description of drawings
Fig. 1 is the utility model device flow chart;
Fig. 2 is the fitting arrangement of the utility model reactor medium ultraviolet lamp and swirl nozzle.
The specific embodiment
Referring to Fig. 1,2, from the flue gas that contains oxysulfide, nitrogen oxide and mercury in the boiler 1 with from the O of ozone generator 3
3The swirl nozzle 4 of flowing through after in agitator 2, mixing sprays into reactor 7.Ozone causes the OH free radical that chain reaction produces strong oxidizing property under the ultraviolet radiation of the uviol lamp that is with quartz socket tube 56 emissions.Hydroxyl radical free radical OH can be rapidly with the SO in the flue gas
2NO and Hg with indissoluble
0Be oxidized to the higher gaseous products SO of dissolubility
3, H
2SO
4, NO
2, HNO
2, HNO
3, Hg (OH)
2With HgO etc., and in the Gas-Liquid Absorption tower 8 of afterbody by the water absorbing and removing, the flue gas after the washing is by chimney 9 dischargings, a spot of Hg that generate in the Gas-Liquid Absorption tower 8
2+Can be through the sulfidion S of mol ratios such as interpolation
2-Catch recovery, and remaining sulfuric acid and nitric acid mixed solution can be used as raw material of industry recycling, whole while desulfurization denitration demercuration process non-secondary pollution.
Swirl nozzle outlet flue gas flow rate need remain on suitable size in the utility model.If swirl nozzle outlet flue gas flow rate is too low; Then can't reach enough even mixing in the reactor; Be unfavorable for fully carrying out of oxidation reaction, if but the outlet flue gas flow rate of swirl nozzle will cause system's crushing to increase too greatly, and then cause system energy consumption to increase.Therefore, the exit velocity of swirl nozzle should remain on 5m/s-30m/s.In addition, swirl nozzle is arranged on the concentric circumference with ultraviolet lamp tube concentric circles alternate intervals and is uniformly distributed with, and places on the diameter line of ultraviolet lamp tube central angle half-angle, and the swirl nozzle center needs to keep equating with the distance at uviol lamp center.
Owing to contain fine particle in the flue gas, if uviol lamp is directly exposed in the flue gas, then uviol lamp is easy to wash away because of the high speed of particle and damages.Therefore, uviol lamp need put the quartz socket tube of being processed by the quartz material of high-penetration light rate at outer surface, the internal diameter of quartz socket tube need be than the external diameter of uviol lamp big 2-4mm, length keeps equating with uviol lamp or is close.
In order to keep in the reactor ultraviolet radiation even, increase the luminous energy effective rate of utilization, it is equal that the spacing b between the uviol lamp must keep, and central angle a also must keep equating.If the layout density of uviol lamp in reactor is too big; Then the flow resistance of flue gas will increase in the reactor; Cause the energy consumption of system to increase; If but uviol lamp arranges that density is too little in the reactor, then be difficult to the ultraviolet radiation intensity that reaches enough, thereby cause the pollutant removing index not reach environmental requirement.Therefore, the optimum range of uviol lamp spacing b and central angle a is respectively 5cm-50cm and 10-45 degree; The uv light irradiation strength relationship is to the size of quantum yield or the productive rate of hydroxyl radical free radical OH.Be difficult to fully to excite ozone to decompose the hydroxyl radical free radical OH oxidation removal pollutant that produces sufficient amount if ultraviolet light irradiation intensity is too little, but if ultraviolet light irradiation intensity is too big, then the application cost of system increases considerably or economy will significantly descend.Therefore, ultraviolet ray intensity need remain on 5W/m
3-200W/m
3, the W/m of unit wherein
3Be meant reactor before uviol lamp is not installed, the needed ultraviolet radiation power of unit volume when reactor is void tower.The size of ultraviolet wavelength has significant effects for photochemical reaction, and ultraviolet wavelength is related to the effective propagation distance of ultraviolet light and the excitation energy size of photon.When ultraviolet wavelength more in short-term, the photon excitation of ultraviolet light can increase relatively, but this moment ultraviolet light propagation distance shorter, the Pollutant Treatment ability that shows as the unit power ultraviolet light is lower.When ultraviolet wavelength is longer; Although the propagation distance of ultraviolet light can increase; But this moment, the excitation energy of ultraviolet light photons significantly reduced, and caused ultraviolet light photons to excite ozone decomposition to discharge the energy shortage of hydroxyl radical free radical OH, finally can cause the removal efficiency of pollutant to be difficult to satisfy environmental requirement.Therefore, the EWL of ultraviolet light should remain in the 160nm-360nm scope.
Ozone is as the releasing agent of hydroxyl radical free radical OH; If dosage is too little, the hydroxyl radical free radical OH quantity that then generates is not enough to abundant oxidation removal pollutant very little; But when the dosage of ozone is too big; Ozone also can cause some side reactions from consuming a large amount of hydroxyl radical free radical OH, cause application cost to increase, and excessive ozone also can bring secondary pollution problems such as ozone leakage.Therefore, the dosage of ozone should remain on 50ppm-1000ppm;
The sulfidion S that adds in the Gas-Liquid Absorption tower
2-Amount need strict control criterion, if excessive interpolation S
2-Will cause secondary pollution and application cost to increase, but S
2-Addition is too little then can to cause the MODEL OF CHEMICAL ABSORPTION PROCESS in the absorption tower abundant inadequately, Hg
2+Capture rate reduce.Therefore, in the practical application, add S
2-Mole should with Hg solution
2+Mole keep to equate, promptly need keep n (S
2-): n (Hg
2+)=1: 1.
Embodiment 2
Embodiment 4
1-4 can find out by the embodiment table, the concentration of ozone, and main technologic parameters such as the ultraviolet radiation power and the time of staying all have remarkable influence to the removal efficiency of pollutant, and under the operating condition shown in the embodiment 1, SO
2, NO and Hg
0The highest removal efficiency respectively up to 98.6%, 92.8% and 100%.This shows that the utility model system has efficiently desulfurization denitration demercuration performance simultaneously, thereby can be used as most preferred embodiment operating parameter of the present invention.
Claims (3)
1. smoke eliminator that combines wet scrubbing based on advanced oxidation; It is characterized in that: be provided with burning and exhaust system that boiler, ozone generator, agitator, swirl nozzle, reactor, Gas-Liquid Absorption tower and chimney constitute, the O that flue gas that boiler combustion produces and ozone generator produce
3Get into the swirl nozzle of flowing through after the mixing in the agitator jointly through pipeline respectively and spray in the reactor that is provided with ultraviolet lamp tube, reactor output gets into the Gas-Liquid Absorption tower through pipeline, and the Gas-Liquid Absorption tower is provided with and adds sulfidion S
2-Import, the discharging that the Gas-Liquid Absorption tower also is provided with mercuric sulphide and sulfuric acid and nitric acid mixed solution is reclaimed mouthful, the exhanst gas outlet of Gas-Liquid Absorption tower gets into smoke stack emission through pipeline.
2. according to the said smoke eliminator that combines wet scrubbing based on advanced oxidation of claim 1; It is characterized in that: ultraviolet lamp tube is arranged on the Reactor inlet end; It is consistent with the reactor import and export flow direction that ultraviolet lamp tube is provided with direction, and the effective ultraviolet radiation power of unit volume is 5W/m in the reactor
3-200W/m
3, the W/m of unit wherein
3Be meant reactor before uviol lamp is not installed, the needed ultraviolet radiation power of unit volume when reactor is void tower; The ultraviolet light EWL is 120nm-360nm.
3. according to the said smoke eliminator that combines wet scrubbing based on advanced oxidation of claim 2; It is characterized in that: when many ultraviolet lamp tubes were set, many ultraviolet lamp tubes were the concentric circles setting, and distance is identical between the neighboring concentric circle; Many ultraviolet lamp tubes are distributed on the circumference of different-diameter; Along same diameter line setting, the central angle between each adjacent two diameter line is identical, and circle centre position is provided with ultraviolet lamp tube; Swirl nozzle is arranged on the concentric circumference with ultraviolet lamp tube concentric circles alternate intervals and is uniformly distributed with, and places on the diameter line of two ultraviolet lamp tube central angle half-angles.
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|---|---|---|---|
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|---|---|---|---|
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| CN106621753A (en) * | 2016-12-26 | 2017-05-10 | 合肥天翔环境工程有限公司 | Ceramic industry kiln furnace desulfurization treatment method |
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| CN108722137A (en) * | 2018-07-02 | 2018-11-02 | 浙江建华集团环保科技有限公司 | A kind of ultraviolet light photooxidation VOCs processors |
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