CN102728215B - Composition and method for removing nitrogen oxides in desulfurizing tower - Google Patents
Composition and method for removing nitrogen oxides in desulfurizing tower Download PDFInfo
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- CN102728215B CN102728215B CN201210260481.0A CN201210260481A CN102728215B CN 102728215 B CN102728215 B CN 102728215B CN 201210260481 A CN201210260481 A CN 201210260481A CN 102728215 B CN102728215 B CN 102728215B
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- desulfurizing tower
- composition
- denitrfying agent
- nitrogen oxide
- flue gas
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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
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- 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 composite denitrfying agent and a method for removing nitrogen oxides from purified flue gas, and in particular relates to a method for forming a mixture with limestone slurry in a desulfurizing tower, desulfurizing the limestone slurry and removing the nitrogen oxides in the composition. The composition is formed by desulfurizing and denitrifying 0.5 to 5 weight parts of denitrfying agent and 100 weight parts of aqueous solution of limestone slurry in the desulfurizing tower, wherein the denitrfying agent consists of a catalyst which accounts for 1.7 to 2.3 weight percent of the denitrfying agent, 10 to 20 percent of oxidant and 78.3 to 87.7 percent of ion solvent; and the denitrfying agent has the pH value of 6 to 8. The composition is injected into the desulfurizing tower through a circulating water injection port or a process water injection port and is in countercurrent contact with the flue gas in the desulfurizing tower for removing the nitrogen oxides. The method can be used for thermal power plants and various combustion boilers which take petroleum and oil as fuel and comprise the desulfurizing tower device, and is used for removing the nitrogen oxides in the flue gas, and 90 percent of emission pollution is reduced. The method has obvious substantive effects.
Description
[technical field]
The present invention relates to composition and the method for the middle nitrogen oxide of purifying flue gas, specifically a kind of composition and method removing nitrogen oxide in desulfurizing tower.
[background technology]
Nitrogen oxide after fossil feedstock burning in exhaust emissions, in an atmosphere through photosynthesis, forms phosgene and pollutes, the main component nitrogen oxide in phosgene.Environmental protection is more and more important and urgent, and the nitrogen oxide discharged after boiler combustion accounts for 70% of total release.Reduce the discharge of nitrogen oxide, being the important means of environmental protect, is the greatest benefit that the mankind improve life condition.
The method of denitration of current employing is solid ammonia selective catalytic reduction (SCR), this technical requirement is at boiler flue gas outlet position, design a set of denitrating system, by 200 DEG C of former flue gases by about high-temperature steam heat exchange to 400 DEG C, spraying ammonia spirit makes NOx in itself and flue gas react, reacted flue gas enters into denitrating tower and reacts with multi-layer solid catalyst vanadic anhydride, is N by NOx conversion
2.Reach the object removing nitrogen oxide, its technical deficiency part is solid catalyst easy in inactivation, and flue gas stream is serious to catalyst erosion, and NH_3 leakage causes secondary pollution, has corrosion to flue rear portion equipment.Denitration efficiency affects by catalysqt deactivation, and average denitration efficiency 68%, equipment investment is high, and operating cost is large.Long-term operation can not the discharge standard of meet the requirement of environmental protection.
The conventional mode removing flue gas has following several:
(1) ammine selectivity catalytic reduction method (SCR): make reducing agent with ammonia at 380 DEG C ~ 400 DEG C, first by ammoniacal liquor and NO
xreaction, then be catalysed and reduced into simple substance N by solid catalyst vanadic anhydride
2.The catalyst easy in inactivation of the method, can be generated as a kind of bonding liquid-hydrogen sulfate ammonia (NH when temperature is low
4hSO
4), catalyst erosion is serious, and reaction linearly declines, and there is potential safety hazard, cannot qualified discharge for a long time.
(2) SNCR method (SNCR): the method is without catalyst, but ammonia, urea consumption are large.And require very high to reaction temperature and the time of staying, be difficult to grasp.
From above denitration technology method, whether the technology of method one is applicable to China's actual conditions, reason be the coal of developed country be Filter Tuber For Clean Coal, and China is raw coal (non-Filter Tuber For Clean Coal), catalyst easy in inactivation is aobvious and should see, catalyst consumption is large, regeneration techniques also under study for action, can not meet discharge standard requirement.
SCR technology is dry method high temperature denitration, and this technology is low temperature wet denitration, and security is good, the feature that temperature range is wide.
(3) lime stone slurry interpolation composition is low-temperature catalytic oxidation denitrfying agent is wet denitration, mainly NO is converted into NO
2and N
2, absorb in desulfurizing tower, denitration can be realized in a mild condition.
[summary of the invention]
In order to solve above-mentioned problem of the prior art and defect, the invention provides a kind of denitration rate high, can invest, in existing desulfurizing tower, add a kind of additive mix with existing desulfurizing agent lime stone slurry, through two kinds of material actings in conjunction, remove sulfur and nitrogen oxides method.
For achieving the above object, design a kind of composition removing nitrogen oxide in desulfurizing tower, comprise the lime stone aqueous solution, metallic catalyst, oxidant, the cation solvent containing percentage by weight 20%, be characterised in that described composition is made up of the denitrfying agent of 0.5 ~ 5 weight portion and the lime stone aqueous solution of 100 weight portions, described denitrfying agent is by 1.7% ~ 2.3% catalyst accounting for denitrfying agent percentage by weight, 10% ~ 20% oxidant, 78.3% ~ 87.7% ion solvent composition, described denitrfying agent pH value is 6-8.
Described catalyst is alkali metal, alkaline-earth metal transition metal-type catalyst.
Described oxidant is the one in potassium manganate or Potassiumiodate or potassium permanganate.
Described cation solvent is violuric acid saline solution.
A kind of method above-mentioned composition being used for desulfurizing tower, comprise desulfurizing tower, desulfurizing tower comprises recirculated water inlet and fresh water (FW) main-inlet, the flue gas containing nitrogen oxide, sulfide is comprised in desulfurizing tower, described composition is it is characterized in that to inject desulfurizing tower through recirculated water inlet or fresh water (FW) inlet, mix with lime stone slurry in desulfurizing tower, the mixed liquor of formation contacts with flue gas adverse current and carries out removing sulphur nitrogen oxide, forms desulphurization denitration double action.Described composition weight: be that the 0.5%-5% of desulfurizing tower sodalime stone slurry weight mixes wherein.
The denitrifying oxide described in method that a kind of above-mentioned composition removes nitrogen oxide comprises the following steps,
3NO
2+H
2O→2HNO
3+NO
NO
2+NO+H
2O→2HNO
2
2NO
2+2HNO
2→2HNO
3+N
2↑
2NO
2+2CaSO
3→2CaSO
4+N
2↑
The present invention is same in afterbody discharging waste gas after boiler combustion, composition and Limestone-gypsum Wet Flue Gas Desulfurization Process tower remove the technology of sulphur nitrogen oxide jointly, denitrfying agent and lime stone slurry are from being mixed into desulfurizing tower, under the condition not increasing any equipment, desulfurizing tower serves a dual purpose, not only desulfurization but also denitration, invest without expensive denitrification apparatus, can reach NO_x removal object.Can effectively remove nitrogen oxide pernicious gas.Method of the present invention can be used for thermal power plant and the various burning boiler (having desulfurizer device) that is fuel with oil coal, for removing nitrogen oxides in effluent, reduces by 90% exhaust emission.There is significant substantial effect.
[detailed description of the invention]
In order to make object of the present invention, technical scheme and advantage clearly understand, the present invention is further elaborated.Production equipment in the application is all the common equipment of this area, should be appreciated that specific embodiment described herein only in order to explain the present invention, is not intended to limit the present invention.
Embodiment:
Composition of the present invention is made up of the lime stone slurry accounting for denitrfying agent and 100 weight portions always forming 0.5 ~ 5 weight portion, forms mixture with lime stone slurry.In desulfuration absorbing tower, the slurries of containing limestone serous are by being dispersed into tiny drop during spray atomizing flue gas and covering the SO of absorbing liquid when contacting with flue gas adverse current in flue gas of the whole section on absorption tower
2absorbed.The NOx mixed in composition denitrfying agent in the lime stone slurry NO(flue gas also simultaneously by spray atomizing selective catalytic oxidation in flue gas has 95% to be insoluble to the NO of liquid for pole, first must change into NO through Catalytic Oxygen
2dissolve in liquid, then generate salt and N through SCR
2).And NO
2be dissolved in liquor and only have the catalyzed redox of part, part NO in addition
2can NO be converted into again, also need could constantly eliminate through catalytic oxidation again, improve the denitration rate that the catalyzed redox of NOx generates salt and nitrogen.Present invention utilizes the Multi-layer sprinkling technology in desulfuration absorbing tower for this reason.The Bian acting in conjunction of composition and lime stone slurry, enhances the additive effect of chemical substance, shields antagonistic effect, and desulfurization/denitration efficiency improves.The stock tank of oxidation neutralization reaction bottom absorption tower of absorbent generates CaSO
4(gypsum), in also helping and HNO
2reaction, can reduce the consumption of composition denitrfying agent.And remaining composition denitrfying agent can not be discharged (composition not with gypsum effect) by gypsum absorption in denitrfying agent, can continue to retain in desulfurizing tower Inner eycle slurries and be recycled, gradually composition denitrfying agent constituent concentration in lime stone slurry can be promoted like this, sustainable progressive denitration intensity, gradually reduces and mixes fresh denitrfying agent supplemental amount.
The present invention is the composition removing nitrogen oxide in desulfurizing tower, comprise the lime stone aqueous solution, metallic catalyst, oxidant, the cation solvent containing percentage by weight 20%, be characterised in that described composition is made up of the denitrfying agent of 0.5 ~ 5 weight portion and the lime stone aqueous solution of 100 weight portions, described denitrfying agent is by 1.7% ~ 2.3% catalyst accounting for denitrfying agent percentage by weight, 10% ~ 20% oxidant, 78.3% ~ 87.7% ion solvent composition, described denitrfying agent pH value is 6-8.
Described catalyst is alkali metal, alkaline-earth metal transition metal-type catalyst.
Described oxidant is the one in potassium manganate or Potassiumiodate or potassium permanganate.
Described cation solvent is violuric acid saline solution.
Method above-mentioned composition being used for desulfurizing tower is as follows, comprise desulfurizing tower, desulfurizing tower comprises recirculated water inlet and fresh water (FW) main-inlet, the flue gas containing nitrogen oxide, sulfide is comprised in desulfurizing tower, described composition is injected desulfurizing tower through recirculated water inlet or fresh water (FW) inlet, mix with lime stone slurry in desulfurizing tower, the mixed liquor of formation contacts with flue gas adverse current and carries out removing sulphur nitrogen oxide, forms desulphurization denitration double action.Described composition weight: be that the denitrfying agent of every 100 weight portion lime stone slurries and 0.5-5 weight portion in desulfurizing tower mixes wherein.
Remove the method for nitrogen oxide with above-mentioned composition, described denitrifying oxide comprises the following steps,
Main reaction process:
2NO+O
2→2NO
2
3NO
2+H
2O→2HNO
3+NO
NO
2+NO+H
2O→2HNO
2
2NO
2+2HNO
2→2HNO
3+N
2↑
2NO
2+2CaSO
3→2CaSO
4+N
2↑
Test result sees the following form:
Claims (3)
1. in desulfurizing tower, remove a method for nitrogen oxide, comprise desulfurizing tower, desulfurizing tower comprises recirculated water inlet and fresh water (FW) inlet, in desulfurizing tower, comprise the flue gas containing nitrogen oxide, sulfide; It is characterized in that the composition removing nitrogen oxide to inject desulfurizing tower through recirculated water inlet or fresh water (FW) inlet, mix with lime stone slurry in desulfurizing tower, the mixed liquor of formation contacts with flue gas adverse current, carries out desulphurization denitration simultaneously;
Described composition is made up of the denitrfying agent of 0.5 ~ 5 weight portion and the lime stone aqueous solution containing percentage by weight 20% of 100 weight portions, described denitrfying agent by account for denitrfying agent percentage by weight 1.7% ~ 2.3% alkali metal, alkaline-earth metal transition metal-type catalyst, 10% ~ 20% oxidant, 78.3% ~ 87.7% cation solvent composition, described denitrfying agent pH value is 6-8
Denitrifying oxide comprises the following steps,
3NO
2+H
2O→2HNO
3+NO
NO
2+NO+H
2O→2HNO
2
2NO
2+2HNO
2→2HNO
3+N
2↑
2NO
2+2CaSO
3→2CaSO
4+N
2↑。
2. in desulfurizing tower, remove as claimed in claim 1 the method for nitrogen oxide, it is characterized in that described oxidant is the one in potassium manganate or Potassiumiodate or potassium permanganate.
3. in desulfurizing tower, remove the method for nitrogen oxide as claimed in claim 1, it is characterized in that described cation solvent is violuric acid saline solution.
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| CN102728215B true CN102728215B (en) | 2015-02-04 |
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| CN105126607B (en) * | 2015-07-31 | 2018-08-31 | 湘潭大学 | A kind of method of denitration and device of regeneration fume from catalytic cracking |
| CN106007087B (en) * | 2016-07-06 | 2018-10-16 | 扬州奇创环保科技有限公司 | A kind of high-concentration ammonia nitrogenous wastewater treatment process and ammonia recovery system |
| CN106731828A (en) * | 2017-02-21 | 2017-05-31 | 毛凡景 | A kind of method for the joint removing of Industrial Stoves desulphurization denitration |
| CN113144849B (en) * | 2021-05-07 | 2023-01-24 | 西安睿宇翰江商贸有限公司 | Denitration agent and denitration solution for smelting flue gas and application of denitration agent and denitration solution |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1317363A (en) * | 2001-03-20 | 2001-10-17 | 华东理工大学 | Process for removing NO2 from waste gas |
| CN101310836A (en) * | 2008-02-25 | 2008-11-26 | 北京博奇电力科技有限公司 | Spray bubbling method all-in-one synergetic desulfurization, denitration, demercuration absorption liquid |
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| CN101590369B (en) * | 2009-06-12 | 2011-06-29 | 浙江天蓝环保技术有限公司 | Mercury removal process based on lime-gypsum method desulphurization system and mercury removal absorption liquid |
| CN102188897B (en) * | 2011-05-11 | 2013-03-13 | 国电科学技术研究院 | Wet flue gas desulfurization and denitrification combined method |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1317363A (en) * | 2001-03-20 | 2001-10-17 | 华东理工大学 | Process for removing NO2 from waste gas |
| CN101310836A (en) * | 2008-02-25 | 2008-11-26 | 北京博奇电力科技有限公司 | Spray bubbling method all-in-one synergetic desulfurization, denitration, demercuration absorption liquid |
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