CN103990362A - Method and device for removing sulfur, nitre and mercury in smoke - Google Patents
Method and device for removing sulfur, nitre and mercury in smoke Download PDFInfo
- Publication number
- CN103990362A CN103990362A CN201410208229.4A CN201410208229A CN103990362A CN 103990362 A CN103990362 A CN 103990362A CN 201410208229 A CN201410208229 A CN 201410208229A CN 103990362 A CN103990362 A CN 103990362A
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- flue gas
- smoke
- chlorine dioxide
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- sulfur
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
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Abstract
The invention relates to a method and a device for removing sulfur, nitre and mercury in smoke. The method comprises the following steps: introducing dedusted smoke into a mixing device, injecting chlorine dioxide gas to carry out gas phase oxidation on the smoke, then introducing the smoke into a wet type sulfur removing device, removing high-valence nitric oxide, sulfur dioxide and HgC12 by taking a calcium-based sulfur removing size as an absorbent, and discharging the clean smoke into the atmosphere; or directly injecting the smoke into the chlorine dioxide gas to carry out gas phase oxidation, then introducing the smoke into a semidry type sulfur removing device, removing high-valence nitric oxide, sulfur dioxide and HgC12 by taking a calcium-based absorbent and humidified fly ash in the smoke as absorbing and removing agents, and discharging the clean smoke into the atmosphere. The method is based on an existing wet type sulfur removing device or semidry type sulfur removing device, thus facilitating the improvement. According to the method and device disclosed by the invention, dust and sulfur do not need to be removed in advance, so that used equipment are reduced, and the complexity of a system is reduced. In addition, an obvious mercury removal effect is also achieved, thereby really embodying the significance of combined removal.
Description
Technical field
The present invention relates to a kind of various pollutants in fume and combine method and the device removing, belong to flue gases purification field.
Background technology
In recent years, atmosphere pollution is for the harm of health and more and more obvious to the threat of ecological environment.China more and more payes attention to for SOx, NOx in flue gas and trace toxic metallic element especially control and the reduction of discharging problem of mercury, and discharge standard is constantly strict, and efficient, economic flue gas purifying technique becomes trend of the times.But in prior art, the equipment that removes complexity, the operating cost of flue gas pollutant is high, how according to existing desulphurization plant installation situation, especially for those middle-size and small-size Industrial Boilers, the high efficiency combined desulfurization and denitration hydrargyrum-removing technology of developing low-cost is significant.
Flue gas desulfurization technique comprises wet method, dry method and semidry method three major types, and wherein wet process of FGD is current main flow technique, the higher and stable performance of its desulfuration efficiency; Semi-dry process flue gas desulphurization is discharged without wastewater and waste acid, and product is easy to process, and wherein the semi-dry method flue gas desulfurization technique such as recirculating fluidized bed, novel all-in-one, gas suspension absorption is all comparatively ripe, single with regard to desulfuration efficiency, desirable not as good as wet desulphurization; And the desulfuration efficiency of dry flue gas desulphurization is lower and sorbent utilization is lower, it seems at present and be still not enough in the face of day by day harsh desulfurization task.
Flue-gas denitration process can be divided into substantially reduction and oxidation absorbs two large classes, and the former utilizes reducing agent etc. that NOx is reduced to N
2, comprising the techniques such as SCR, SNCR, carbon fiber adsorption and catalytic combustion, the latter utilizes strong oxidizer or living radical that the NO of indissoluble is oxidized to higher nitrogen oxides, thus later stage and SO
xremove simultaneously.Comparatively speaking, oxidation absorption method of denitration flexible operation and system are comparatively simple, wherein chlorine dioxide (ClO
2) a kind of as oxidant, seldom, and research is mostly round aqueous solution of chlorine dioxide liquid phase oxidation NO, the technique that oxidation product removes through wet absorption in research.
For example CN1293933C, CN1304089C, these four patents of CN101745305A, CN101385942B, be all the waste gas purification problem about containing SOx and NOx, all relates to the NO in aqueous solution of chlorine dioxide oxidation gaseous effluent.This kind of technique is to utilize Oxygen in Liquid agent to be oxidized NO, then utilizes the high valence state NOx of alkali liquor absorption.This technique needs design apparatus to remove in advance SO
2, need in addition separately to add alkali lye and carry out NO_x removal, can make system more complicated so on the one hand, also can increase operating cost on the other hand, and not there is associating demercuration performance.For hydrogen peroxide with low cost, its oxidation susceptibility is the generation for free radical, and this makes in this kind of oxidation technology, and flue gas needs first through dedusting, to avoid the impact on free radical average life of particle in flue gas.
According to United Nations Environment Programme (UNEP) data, show, approximately 5000 tons of mercury contaminants are discharged every year in the whole world in atmosphere, and wherein artificial mercury emission is approximately 1930 tons, and fire coal is the important component part in artificial mercury emissions source, accounts for 45%.Power plant is as coal-fired rich and influential family, and its mercury emissions problem is day by day subject to people and pays close attention to.Mercury in coal-fired flue-gas mainly comprises three kinds of forms: Elemental Mercury (Hg
0), oxidation state mercury (Hg
2+) and particle mercury (Hg
p).Particle mercury (Hg
p) can be removed by cleaners such as electrostatic precipitation and bag-type dusts oxidation state mercury (Hg
2+) can or efficiently remove by existing desulfurizer by flying dust adsorbing and removing in flue gas.And Elemental Mercury (Hg
0) owing to thering is stronger insoluble and stability, be difficult to remove.Therefore, in coal-fired plant flue gas, the removal efficiency of mercury greatly depends on the form that exists of mercury, utilizes chlorine dioxide by Elemental Mercury (Hg
0) be oxidized to oxidation state mercury (Hg
2+), just can utilize existing wet method or semidry process desulfurizer that mercury is efficiently removed.
Summary of the invention
The method and the device that the object of this invention is to provide a kind of flue gas desulfurization and denitrification demercuration, utilize chlorine dioxide gas phase direct oxidation NO and Elemental Mercury (Hg
0), downstream is through wet method or semidry process desulfurizer cooperation-removal NOx, SOx and oxidation state mercury (Hg
2+), realize the technology of efficient combined desulfurization and denitration demercuration.
The technical scheme that the present invention takes is:
The method of flue gas desulfurization and denitrification demercuration: by entering mixing arrangement after flue gas ash removal, spray into a chlorine dioxide gaseous oxidation, then flue gas enter wet desulphurization device using limestone-gypsum slurries as absorbent remove high price nitrogen oxide, sulfur dioxide and HgCl
2, clean flue gas enters atmosphere by chimney; Or flue gas is directly sprayed into chlorine dioxide gaseous oxidation, and then flue gas enters semidry process desulfurizer with Ca (OH)
2as absorbing and removing, agent removes nitrogen oxide, sulfur dioxide and the HgCl of high price with flying dust after humidification in flue gas
2, clean flue gas enters atmosphere by chimney.
A kind of device of flue gas desulfurization and denitrification demercuration, comprise smoke inlet pipe, smoke inlet pipe communicates with gas mixer by deduster and blower fan, gas mixer is connected with chlorine dioxide preparing apparatus, gas mixer gas outlet connects wet desulphurization device, and wet desulphurization device and chimney join.
A kind of device of flue gas desulfurization and denitrification demercuration, comprise smoke inlet pipe, smoke inlet pipe is all connected with gas mixer with chlorine dioxide preparing apparatus, and gas mixer gas outlet connects semidry process desulfurizer, and semidry process desulfurizer is connected with chimney by deduster and blower fan.
Certain density chlorine dioxide is injected into gas mixer to be mixed with flue gas, and its strong oxidizing property can be the nitrogen oxide that high valence state easily removes by NO efficient oxidation under the cigarette temperature of 70 ℃～150 ℃, also can be by Elemental Mercury (Hg
0) be oxidized to the oxidation state mercury being easily removed, and because the HCl in product is with HgCl
2form be present in flue gas, the gas passing into should meet the mol ratio [ClO of the NO in chlorine dioxide and flue gas
2]: [NO], at 0.47～1.57 o'clock, can realize the oxidation efficiency of NO between 59%～100%.
If pre-oxidation district combined downstream wet desulphurization device, limestone-gypsum slurries are as absorbent, thereby the nitrogen oxide of high price will react with unreacted desulfurization slurry generation, calcium nitrate will be removed, HgCl
2dissolve in desulfurization slurry and be removed, clean flue gas enters atmosphere by chimney.
If pre-oxidation district combined downstream semidry process desulfurizer, Ca (OH)
2with the flying dust after humidification in flue gas as absorbing and removing agent, Ca (OH) wherein
2the downstream in Shi pre-oxidation district sprays into flue with slurries form, and the nitrogen oxide of high price will generate calcium nitrate with unreacted reactive desulfurizing agent, vaporize dry, and then will remove, most HgCl along with the absorption of flue gas heat
2can be by Ca (OH)
2absorbing and removing.Flue gas can be separated the particulate solid in flue gas by dust arrester, and clean flue gas enters atmosphere by chimney.
Technique of the present invention is to utilize chlorine dioxide selectively by the NO in flue gas and Elemental Mercury (Hg
0) be oxidized to respectively the mercury (Hg that the nitrogen oxide of high valence state and oxidation state easily absorb
2+), and chlorine dioxide hardly with SO
2reaction, then combines and removes oxidation product and SOx in conjunction with the wet method in downstream or semidry process desulfurizer, forms main gas pollutant SOx, NOx and mercury in flue gas truly and combines the technique removing.The advantage of this kind of technique is, based on existing wet desulphurization device or semidry process desulfurizer, conveniently transforms; Without dedusting in advance, also, without desulfurization in advance, can reduce equipment, reduce the complexity of system; Also have in addition obvious demercuration effect, really embody and combine the meaning removing.
Accompanying drawing explanation
Fig. 1 is the apparatus structure schematic diagram of the flue gas desulfurization and denitrification demercuration of the embodiment of the present invention 1.
Fig. 2 is the apparatus structure schematic diagram of the flue gas desulfurization and denitrification demercuration of the embodiment of the present invention 2.
Wherein: 1, chlorine dioxide preparing apparatus; 2, gas mixer; 3, wet desulphurization device; 4, deduster; 5, blower fan; 6, chimney; 7, semidry process desulfurizer.
The specific embodiment
The present invention is based on existing wet method or semidry process desulfurizer and realize flue gas combined desulfurization and denitration demercuration in conjunction with chlorine dioxide gaseous oxidation, below in conjunction with embodiment, this is described further.
Embodiment 1
As Fig. 1, a kind of device of flue gas desulfurization and denitrification demercuration, comprise smoke inlet pipe, smoke inlet pipe communicates with gas mixer 2 by deduster 4 and blower fan 5, gas mixer 2 is connected with chlorine dioxide preparing apparatus 1, gas mixer 2 gas outlets connect wet desulphurization device 3, and wet desulphurization device 3 joins with chimney 6.
In implementing the technical process of the present embodiment, the chlorine dioxide that chlorine dioxide preparing apparatus 1 is prepared sprays into the gas mixer 2 of wet desulphurization device 3 front portions, at this, realizes NO and the Elemental Mercury (Hg in the flue gas after deduster 4 dedustings
0) pre-oxidation, the NO in flue gas is oxidized to high valence state nitrogen oxide, by Elemental Mercury (Hg
0) be oxidized to oxidation state mercury (Hg
2+), with HgCl
2form exist with flue gas in, the flue gas after pre-oxidation enters wet desulphurization device 3 subsequently, limestone-gypsum slurries when removing SOx, the nox adsorption of the high valence state that Jiang pre-oxidation district obtains by HgCl
2dissolving realizes combined desulfurization and denitration demercuration, and desulphurization and denitration, demercuration product all enter waste liquid, and the clean flue gas after purification enters atmosphere through chimney 6.
Embodiment 2
As Fig. 2, a kind of device of flue gas desulfurization and denitrification demercuration, comprise smoke inlet pipe, smoke inlet pipe is all connected with gas mixer 2 with chlorine dioxide preparing apparatus 1, gas mixer 2 gas outlets connect semidry process desulfurizer 7, and semidry process desulfurizer 7 is connected with chimney 6 by deduster 4 and blower fan 5.
In implementing the technical process of the present embodiment, the chlorine dioxide that chlorine dioxide preparing apparatus 1 is prepared sprays into the gas mixer 2 of semidry process desulfurizer 7 front portions, at this, realize the pre-oxidation of flue gas, the NO in flue gas is oxidized to high valence state nitrogen oxide, by Elemental Mercury (Hg
0) be oxidized to oxidation state mercury (Hg
2+), with HgCl
2form exist with flue gas in, the flue gas after pre-oxidation enters semidry process desulfurizer 7 subsequently, flue gas is through Ca (OH)
2the spraying area of slurries, a large amount of Ca (OH)
2slurries fully contact with flue gas, and the nox adsorption of the SOx in flue gas, high valence state is removed, and slurries absorb flue gas heat simultaneously, dry through overflash, form solid-state desulphurization and denitration product, the flying dust in particle and Ca (OH)
2deng by efficient adsorption oxidation state mercury (Hg
2+), the research relevant for chlorine element for mercury removal shows, HgCl
2can be by Ca (OH)
2efficient absorption removes, and has completed thus in flue gas SOx, NOx and has removed combining of mercury, and the flue gas after purification is carrying particle and entering deduster 4 and remove after particle, and final clean flue gas is discharged in atmosphere through chimney 6.
Claims (5)
1. the method for a flue gas desulfurization and denitrification demercuration, it is characterized in that, by entering mixing arrangement after flue gas ash removal, spray into chlorine dioxide gaseous oxidation, then flue gas enter wet desulphurization device using limestone-gypsum slurries as absorbent remove high price nitrogen oxide, sulfur dioxide and HgCl
2, clean flue gas enters atmosphere by chimney; Or flue gas is directly sprayed into chlorine dioxide gaseous oxidation, and then flue gas enters semidry process desulfurizer with Ca (OH)
2as absorbing and removing, agent removes nitrogen oxide, sulfur dioxide and the HgCl of high price with flying dust after humidification in flue gas
2, clean flue gas enters atmosphere by chimney.
2. the method for a kind of flue gas desulfurization and denitrification demercuration according to claim 1, is characterized in that, described chlorine dioxide straying quatity should meet the mol ratio [ClO of NO in chlorine dioxide and flue gas
2]: [NO] is 0.47～1.57:1.
3. the method for a kind of flue gas desulfurization and denitrification demercuration according to claim 1, is characterized in that, described chlorine dioxide sprays into the flue-gas temperature of position at 70～150 ℃.
4. the device of a flue gas desulfurization and denitrification demercuration, comprise smoke inlet pipe, it is characterized in that, smoke inlet pipe communicates with gas mixer by deduster and blower fan, gas mixer is connected with chlorine dioxide preparing apparatus, gas mixer gas outlet connects wet desulphurization device, and wet desulphurization device and chimney join.
5. the device of a flue gas desulfurization and denitrification demercuration, comprise smoke inlet pipe, it is characterized in that, smoke inlet pipe is all connected with gas mixer with chlorine dioxide preparing apparatus, gas mixer gas outlet connects semidry process desulfurizer, and semidry process desulfurizer is connected with chimney by deduster and blower fan.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410208229.4A CN103990362A (en) | 2014-05-16 | 2014-05-16 | Method and device for removing sulfur, nitre and mercury in smoke |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410208229.4A CN103990362A (en) | 2014-05-16 | 2014-05-16 | Method and device for removing sulfur, nitre and mercury in smoke |
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| Publication Number | Publication Date |
|---|---|
| CN103990362A true CN103990362A (en) | 2014-08-20 |
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ID=51304845
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|---|---|---|---|
| CN201410208229.4A Pending CN103990362A (en) | 2014-05-16 | 2014-05-16 | Method and device for removing sulfur, nitre and mercury in smoke |
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Cited By (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104437037A (en) * | 2014-12-19 | 2015-03-25 | 山东山大华特环保工程有限公司 | Low-temperature fume oxidizing and denitration method and system |
| CN104743727A (en) * | 2015-03-27 | 2015-07-01 | 山东大学 | System and method for cooperatively removing mercury with desulfurization waste water |
| CN104984656A (en) * | 2015-06-23 | 2015-10-21 | 哈尔滨工业大学 | Multistage internal circulation semi-dry method desulfurization, denitrification and demercuration integrated device |
| CN106076106A (en) * | 2016-08-02 | 2016-11-09 | 山东大学 | A kind of semi-dry desulfurization and denitrification system and method based on biomass ash |
| CN106139792A (en) * | 2015-04-23 | 2016-11-23 | 沈阳铝镁科技有限公司 | A kind of baking flue gas governing system and administering method |
| CN108014613A (en) * | 2016-11-02 | 2018-05-11 | 煤科院节能技术有限公司 | A kind of damp dry type flue gas purifying system and method based on Carbon Materials oxidation and denitration |
| CN111545024A (en) * | 2020-03-25 | 2020-08-18 | 南京中电环保科技有限公司 | Oxidation system and method for flue gas NOx |
| CN111773923A (en) * | 2020-06-29 | 2020-10-16 | 山东神华山大能源环境有限公司 | Low-temperature tail gas treatment system and treatment process for engine emission test |
| CN112898068A (en) * | 2019-12-04 | 2021-06-04 | 超重力有限公司 | Method for producing solid nitrogen fertilizer |
| WO2021134926A1 (en) * | 2019-12-30 | 2021-07-08 | 童裳慧 | Desulfurization and denitration method using chlorine dioxide |
| CN113117488A (en) * | 2019-12-30 | 2021-07-16 | 中晶环境科技股份有限公司 | Integrated process for preparing cementing material by utilizing chlorine dioxide for desulfurization and denitrification |
| CN113117482A (en) * | 2019-12-30 | 2021-07-16 | 中晶环境科技股份有限公司 | Method for desulfurization and denitrification by using gas-phase oxidant |
| CN113117510A (en) * | 2019-12-31 | 2021-07-16 | 可徕卡（上海）环境科技有限公司 | Flue gas desulfurization and denitrification method based on sodium bisulfite |
| CN113117487A (en) * | 2019-12-30 | 2021-07-16 | 中晶环境科技股份有限公司 | Process for simultaneously desulfurizing and denitrifying flue gas |
| CN113117486A (en) * | 2019-12-30 | 2021-07-16 | 中晶环境科技股份有限公司 | Integrated treatment method for flue gas desulfurization and denitrification and cementing material preparation |
| CN113117477A (en) * | 2019-12-30 | 2021-07-16 | 中晶环境科技股份有限公司 | Integrated process for treating flue gas and preparing cementing material |
| CN113117501A (en) * | 2019-12-31 | 2021-07-16 | 可徕卡（上海）环境科技有限公司 | Flue gas treatment method |
| CN113634100A (en) * | 2020-05-11 | 2021-11-12 | 上海梅山钢铁股份有限公司 | Method for carrying out oxidation denitration on sintering flue gas by using chlorine dioxide |
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| CN104437037A (en) * | 2014-12-19 | 2015-03-25 | 山东山大华特环保工程有限公司 | Low-temperature fume oxidizing and denitration method and system |
| CN104743727A (en) * | 2015-03-27 | 2015-07-01 | 山东大学 | System and method for cooperatively removing mercury with desulfurization waste water |
| CN104743727B (en) * | 2015-03-27 | 2017-06-06 | 山东大学 | A kind of desulfurization wastewater cooperates with the System and method for of demercuration |
| CN106139792A (en) * | 2015-04-23 | 2016-11-23 | 沈阳铝镁科技有限公司 | A kind of baking flue gas governing system and administering method |
| CN104984656A (en) * | 2015-06-23 | 2015-10-21 | 哈尔滨工业大学 | Multistage internal circulation semi-dry method desulfurization, denitrification and demercuration integrated device |
| CN106076106A (en) * | 2016-08-02 | 2016-11-09 | 山东大学 | A kind of semi-dry desulfurization and denitrification system and method based on biomass ash |
| CN108014613A (en) * | 2016-11-02 | 2018-05-11 | 煤科院节能技术有限公司 | A kind of damp dry type flue gas purifying system and method based on Carbon Materials oxidation and denitration |
| CN112898068A (en) * | 2019-12-04 | 2021-06-04 | 超重力有限公司 | Method for producing solid nitrogen fertilizer |
| WO2021134926A1 (en) * | 2019-12-30 | 2021-07-08 | 童裳慧 | Desulfurization and denitration method using chlorine dioxide |
| CN113117488A (en) * | 2019-12-30 | 2021-07-16 | 中晶环境科技股份有限公司 | Integrated process for preparing cementing material by utilizing chlorine dioxide for desulfurization and denitrification |
| CN113117482A (en) * | 2019-12-30 | 2021-07-16 | 中晶环境科技股份有限公司 | Method for desulfurization and denitrification by using gas-phase oxidant |
| CN113117487A (en) * | 2019-12-30 | 2021-07-16 | 中晶环境科技股份有限公司 | Process for simultaneously desulfurizing and denitrifying flue gas |
| CN113117486A (en) * | 2019-12-30 | 2021-07-16 | 中晶环境科技股份有限公司 | Integrated treatment method for flue gas desulfurization and denitrification and cementing material preparation |
| CN113117481A (en) * | 2019-12-30 | 2021-07-16 | 中晶环境科技股份有限公司 | Method for desulfurization and denitrification by using chlorine dioxide |
| CN113117477A (en) * | 2019-12-30 | 2021-07-16 | 中晶环境科技股份有限公司 | Integrated process for treating flue gas and preparing cementing material |
| JP2022541800A (en) * | 2019-12-30 | 2022-09-27 | 中晶環境科技股▲ふん▼有限公司 | Desulfurization/denitrification method using chlorine dioxide |
| CN113117510A (en) * | 2019-12-31 | 2021-07-16 | 可徕卡（上海）环境科技有限公司 | Flue gas desulfurization and denitrification method based on sodium bisulfite |
| CN113117501A (en) * | 2019-12-31 | 2021-07-16 | 可徕卡（上海）环境科技有限公司 | Flue gas treatment method |
| CN111545024A (en) * | 2020-03-25 | 2020-08-18 | 南京中电环保科技有限公司 | Oxidation system and method for flue gas NOx |
| CN113634100A (en) * | 2020-05-11 | 2021-11-12 | 上海梅山钢铁股份有限公司 | Method for carrying out oxidation denitration on sintering flue gas by using chlorine dioxide |
| CN111773923A (en) * | 2020-06-29 | 2020-10-16 | 山东神华山大能源环境有限公司 | Low-temperature tail gas treatment system and treatment process for engine emission test |
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Application publication date: 20140820 |