CN106237807A - A kind of method for coal-fired flue-gas simultaneous SO_2 and NO removal - Google Patents

A kind of method for coal-fired flue-gas simultaneous SO_2 and NO removal Download PDF

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Publication number
CN106237807A
CN106237807A CN201610810426.2A CN201610810426A CN106237807A CN 106237807 A CN106237807 A CN 106237807A CN 201610810426 A CN201610810426 A CN 201610810426A CN 106237807 A CN106237807 A CN 106237807A
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China
Prior art keywords
flue gas
regeneration
gas
absorbing liquid
liquid
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CN201610810426.2A
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Chinese (zh)
Inventor
程广文
姚明宇
李阳
杨成龙
杨嵩
付康丽
赵婷雯
赵瀚辰
蔡铭
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Xian Thermal Power Research Institute Co Ltd
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Xian Thermal Power Research Institute Co Ltd
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Priority to CN201610810426.2A priority Critical patent/CN106237807A/en
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D53/00Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34Chemical or biological purification of waste gases
    • B01D53/74General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/76Gas phase processes, e.g. by using aerosols
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D53/00Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/14Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by absorption
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D53/00Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34Chemical or biological purification of waste gases
    • B01D53/46Removing components of defined structure
    • B01D53/60Simultaneously removing sulfur oxides and nitrogen oxides
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D2251/00Reactants
    • B01D2251/10Oxidants
    • B01D2251/104Ozone
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D2252/00Absorbents, i.e. solvents and liquid materials for gas absorption
    • B01D2252/20Organic absorbents
    • B01D2252/205Other organic compounds not covered by B01D2252/00 - B01D2252/20494
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D2257/00Components to be removed
    • B01D2257/40Nitrogen compounds
    • B01D2257/404Nitrogen oxides other than dinitrogen oxide
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02ATECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A50/00TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
    • Y02A50/20Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters

Abstract

The invention discloses a kind of method for coal-fired flue-gas simultaneous SO_2 and NO removal, first, allow former flue gas pass through the preposition zoneofoxidation of NO, in this region, the NO in flue gas and the outside O sprayed into3Oxidation reaction is occurred to generate NO2, wherein O3Straying quatity and flue gas in the mol ratio of NO be 1.1:1, the flue gas through zoneofoxidation subsequently enters eluting column, in tower flue gas and absorbing liquid to lower and on inversely contact, the SO in flue gas2And NO2Being absorbed by liquid absorption at a set temperature, last neat stress is got rid of from tower top;After desulfuration efficiency or denitration efficiency reduce, absorbing liquid is got rid of bottom eluting column, enter regeneration of absorption solution system, in regeneration of absorption solution system, first use in ammonia and absorbing liquid is to proper pH value, after then concentration, room temperature crystallize to expection solid content, centrifugation again, and then obtaining regeneration of ionic liquid and by-product ammonium nitrate and ammonium sulfate, regeneration of ionic liquid enters eluting column and is circulated utilization, by-product ammonium nitrate and ammonium sulfate as chemical fertilizer.

Description

A kind of method for coal-fired flue-gas simultaneous SO_2 and NO removal
Technical field:
The invention belongs to atmosphere pollution Treatment process field, be specifically related to a kind of for coal-fired flue-gas simultaneous SO_2 and NO removal Method.
Background technology:
SO2It is the Air Pollutants of discharged from coal-fired boiler with NO, human health and natural environment are caused greatly Threaten.Coal-fired flue gas desulfurization and denitration is always the emphasis that atmosphere pollution is administered.At present, industrial flue gas desulfurization mainly uses stone Lime stone-gypsum, denitrating flue gas mainly uses SCR method.Two kinds of methods are respectively provided with higher pollutant removing efficiency, but due to often Kind of pollutant all use single removing system and technique, cause that floor space is big, investment operating cost is high.Meanwhile, above-mentioned side Method also can produce a large amount of solid waste pollutant (waste and old SCR catalyst and Gypsum Fibrosum).Therefore in the urgent need to developing novel SO2Take off with NO Except technology.
Wet flue gas simultaneous SO_2 and NO removal is a kind of novel pollutant removing technology, receives significant attention in recent years.Should The basic ideas of technology are first NO in flue gas to be oxidized to NO2, then utilize exclusive absorbing liquid by SO in same system2And NO2 Removing, thus reach the purpose of simultaneous SO_2 and NO removal.Wherein, exclusive absorbing liquid is the core skill of wet flue gas simultaneous SO_2 and NO removal Art.At present, modal absorbing liquid is ammonia (or liquefied ammonia).But carry out simultaneous SO_2 and NO removal with ammonia as absorbing liquid to there is ammonia and escape Ease (ammonia damages) is big, the shortcoming such as aeroge concentration height in tail gas, substantially increases pollutant removing cost and is easily generated secondary simultaneously Pollute.Therefore, develop a kind of Novel desulphurization denitration absorbing liquor and corresponding pollutant simultaneous removing technology seems particularly Necessary and important.
Summary of the invention:
It is an object of the invention to the shortcoming overcoming above-mentioned prior art, it is provided that a kind of for coal-fired flue-gas desulfurization simultaneously The method of denitration.
For reaching above-mentioned purpose, the present invention adopts the following technical scheme that and realizes:
A kind of method for coal-fired flue-gas simultaneous SO_2 and NO removal, first, allows former flue gas pass through the preposition zoneofoxidation of NO, at this Region, the NO in flue gas and the outside O sprayed into3Oxidation reaction is occurred to generate NO2, wherein O3Straying quatity and the rubbing of NO in flue gas You are than being 1.1:1, and the flue gas through zoneofoxidation subsequently enters eluting column, in tower flue gas and absorbing liquid to lower and on inversely connect Touch, the SO in flue gas2And NO2Being absorbed by liquid absorption at a set temperature, last neat stress is got rid of from tower top;
After desulfuration efficiency or denitration efficiency reduce, absorbing liquid is got rid of bottom eluting column, enter regeneration of absorption solution system System, in regeneration of absorption solution system, first uses in ammonia and absorbing liquid is to proper pH value, and then concentration, room temperature crystallize to expection After solid content, then centrifugation, and then obtaining regeneration of ionic liquid and by-product ammonium nitrate and ammonium sulfate, regeneration of ionic liquid enters Enter eluting column and be circulated utilization, by-product ammonium nitrate and ammonium sulfate as chemical fertilizer.
The present invention is further improved by: in described eluting column absorbing liquid be mass fraction be the ionic liquid of 5~10% Body aqueous solution, wherein, ionic liquid is any one in ethanolamine lactate, ethanolamine formates and ethanolamine acetate.
The present invention is further improved by: in described eluting column, absorbing liquid temperature is 40~60 DEG C.
The present invention is further improved by: in described eluting column, flue gas and absorbing liquid time of contact are 3~5s.
The present invention is further improved by: in described eluting column, liquid-gas ratio is: 10~20L/m3
The present invention is further improved by: in described regeneration of absorption solution system, with in ammonia and absorbing liquid to pH be 8~ 9。
The present invention is further improved by: in described regeneration of absorption solution system, with in ammonia and after absorbing liquid, will absorb After liquid condensing crystallizing is 10~15% to solid content, then it is centrifuged separating.
Compared with prior art, there is advantages that
(1) replace ammonia to make absorbing liquid with the ionic liquid that vapour pressure is extremely low, the loss of absorbing liquid can be significantly reduced;By ammonia Water removal absorption system, only as nertralizer for the regeneration of absorbing liquid, it is to avoid the product of the gentle gel problem of the escaping of ammonia Raw, at utmost reduce the usage amount of ammonia simultaneously.These each contribute to reduce denitration desulphurization cost, reduce secondary pollution and send out Raw.
(2) with ionic liquid aqueous solution rather than the higher pure ionic liquid of viscosity makees absorbing liquid, it is possible to decrease operating cost;With " ammonia neutralization+condensing crystallizing+centrifugation " technology and unconventional " high-temperature pressure-reduction desorbing " technology regeneration of ionic liquid, not only Capable of reducing energy consumption, and ammonium sulfate and ammonium nitrate can be obtained, make desulphurization denitration by-product get utilization.
Accompanying drawing illustrates:
The wet flue gas simultaneous SO_2 and NO removal schematic diagram that Fig. 1 provides for the present invention.
The wet flue gas simultaneous SO_2 and NO removal process chart that Fig. 2 provides for the present invention.
Detailed description of the invention:
Below in conjunction with specific embodiment, the present invention is described in further detail, described in be explanation of the invention and It not to limit.
A kind of method for coal-fired flue-gas simultaneous SO_2 and NO removal of the present invention, the method includes: the preposition oxidation of NO, ionic liquid Body (IL, AmBn) absorb NO simultaneously2And SO2, the technique such as ammonia regeneration of ionic liquid, its removing principle is as shown in Figure 1.Can from Fig. 1 Know, this simultaneous SO_2 and NO removal method that the present invention provides with the ionic liquid of a kind of " green " environmental protection as absorbing liquid.Due to from Sub-liquid vapour forces down, dissolubility is good, chemically and thermally stability high, absorbing liquid is free of losses during pollutant removing.Ammonia Being intended only as the acid-base neutralization agent regeneration for ionic liquid, can not enter flue gas system, therefore, the most there is not the escaping of ammonia in this method And aeroge problem.Additionally, with ammonia regeneration obtain ionic liquid can huge profit use, the ammonium salt obtained can be as fertilizer application.
For achieving the above object, the technical solution used in the present invention (see Fig. 2) is:
First, allow former flue gas pass through the preposition zoneofoxidation of NO, in this region, the NO in flue gas and the outside O sprayed into3There is oxygen Change reaction and generate NO2, wherein O3Straying quatity and flue gas in the mol ratio of NO be 1.1:1, the flue gas through zoneofoxidation subsequently enters Eluting column, in tower flue gas and absorbing liquid to lower and on inversely contact, the SO in flue gas2And NO2Absorbed liquid at a set temperature Absorbing, last neat stress is got rid of from tower top;After desulfuration efficiency or denitration efficiency reduce, absorbing liquid is arranged bottom eluting column Remove, enter regeneration of absorption solution system.In regeneration of absorption solution system, first use in ammonia and absorbing liquid is to proper pH value, then After concentration, room temperature crystallize to expection solid content, then centrifugation, regeneration of ionic liquid and by-product ammonium nitrate and sulfur can be obtained Acid ammonium, regeneration of ionic liquid enters eluting column and is circulated utilization, and by-product can be used as chemical fertilizer.
In described eluting column absorbing liquid (fresh) be mass fraction be the ionic liquid aqueous solution of 5~10%, wherein, ion Liquid is any one in ethanolamine lactate, ethanolamine formates and ethanolamine acetate.
In described eluting column, absorbing liquid temperature is 40~60 DEG C.
In described eluting column, flue gas and absorbing liquid time of contact are 3~5s.
In described eluting column, liquid-gas ratio is: 10~20L/m3
In described regeneration of absorption solution system, with in ammonia and absorbing liquid is 8~9 to pH.
In described regeneration of absorption solution system, with in ammonia and after absorbing liquid, it is 10 by absorbing liquid condensing crystallizing to solid content ~after 15%, then it is centrifuged separating.
SO in former flue gas and neat stress is tested respectively with flue gas analyzer testo 3502And NO concentration, calculate de-by formula 1 Sulphur efficiency and denitration efficiency.
η=(cFormer-cOnly)/cFormer× 100% formula 1
In formula 1, η represents desulfuration efficiency or denitration efficiency, cFormerRepresenting SO2 or NO concentration in former flue gas, unit is mg/ m3;cOnlyRepresenting SO2 or NO concentration in former flue gas, unit is mg/m3
Embodiment
The present embodiment Central Plains flue gas is simulated flue gas, and total flow is 6L/min, consists of: 1000ppm SO2, 300ppm NO, 4% (v/v) O2, N2For carrier gas.
First, allow former flue gas by the preposition zoneofoxidation of NO.In this region, NO and the outside O sprayed in flue gas3Aoxidize Reaction generates NO2, wherein O3Straying quatity and flue gas in the mol ratio of NO be 1.1:1.Flue gas through zoneofoxidation subsequently enters pouring Wash tower, in tower flue gas and absorbing liquid to lower and on inversely contact, the SO in flue gas2And NO2It is absorbed by liquid absorption at 40 times, Rear neat stress is got rid of from the top of tower.After desulfuration efficiency or denitration efficiency reduce, absorbing liquid is got rid of bottom eluting column, enters Enter regeneration of absorption solution system.In regeneration of absorption solution system, first use in ammonia and absorbing liquid is to proper pH value, then concentrate, After room temperature crystallizes to expection solid content, then centrifugation, regeneration of ionic liquid and the by-product such as ammonium nitrate and ammonium sulfate can be obtained Thing.Regeneration of ionic liquid enters eluting column and recycles, and by-product can be used as chemical fertilizer.
Instantiation

Claims (7)

1. the method for coal-fired flue-gas simultaneous SO_2 and NO removal, it is characterised in that: first, allow former flue gas by the preposition oxygen of NO Change district, in this region, the NO in flue gas and the outside O sprayed into3Oxidation reaction is occurred to generate NO2, wherein O3Straying quatity and flue gas The mol ratio of middle NO is 1.1:1, and the flue gas through zoneofoxidation subsequently enters eluting column, in tower flue gas and absorbing liquid to lower and on Reverse contact, the SO in flue gas2And NO2Being absorbed by liquid absorption at a set temperature, last neat stress is got rid of from tower top;
After desulfuration efficiency or denitration efficiency reduce, absorbing liquid is got rid of bottom eluting column, enter regeneration of absorption solution system, In regeneration of absorption solution system, first using in ammonia and absorbing liquid is to proper pH value, then concentration, room temperature crystallize to expection solid content After, then centrifugation, and then obtaining regeneration of ionic liquid and by-product ammonium nitrate and ammonium sulfate, regeneration of ionic liquid enters drip washing Tower is circulated utilization, by-product ammonium nitrate and ammonium sulfate and is used as chemical fertilizer.
2. according to a kind of method for coal-fired flue-gas simultaneous SO_2 and NO removal described in claims 1, it is characterised in that: described In eluting column absorbing liquid be mass fraction be the ionic liquid aqueous solution of 5~10%, wherein, ionic liquid is ethanolamine lactic acid Any one in salt, ethanolamine formates and ethanolamine acetate.
3. according to a kind of method for coal-fired flue-gas simultaneous SO_2 and NO removal described in claims 1, it is characterised in that: described In eluting column, absorbing liquid temperature is 40~60 DEG C.
4. according to a kind of method for coal-fired flue-gas simultaneous SO_2 and NO removal described in claims 1, it is characterised in that: described In eluting column, flue gas and absorbing liquid time of contact are 3~5s.
5. according to a kind of method for coal-fired flue-gas simultaneous SO_2 and NO removal described in claims 1, it is characterised in that: described In eluting column, liquid-gas ratio is: 10~20L/m3
6. according to a kind of method for coal-fired flue-gas simultaneous SO_2 and NO removal described in claims 1, it is characterised in that: described In regeneration of absorption solution system, with in ammonia and absorbing liquid is 8~9 to pH.
7. according to a kind of method for coal-fired flue-gas simultaneous SO_2 and NO removal described in claims 1, it is characterised in that: described In regeneration of absorption solution system, with in ammonia and after absorbing liquid, after absorbing liquid condensing crystallizing to solid content is 10~15%, then enter Row centrifugation.
CN201610810426.2A 2016-09-08 2016-09-08 A kind of method for coal-fired flue-gas simultaneous SO_2 and NO removal Pending CN106237807A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107198937A (en) * 2017-05-08 2017-09-26 西安热工研究院有限公司 A kind of method of wet process of FGD
CN109126417A (en) * 2018-08-01 2019-01-04 深圳前海中盛环保科技有限公司 The method of industrial smoke synchronized desulfuring and denitrifying

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1698929A (en) * 2005-05-09 2005-11-23 中国科学院过程工程研究所 Functionalized ion liquid of alcoholamine carboxylate
US20140294718A1 (en) * 2013-03-29 2014-10-02 Korea Institute Of Science And Technology Novel sulfur dioxide and/or sulfur dioxide hydrate absorbent
CN205461713U (en) * 2016-03-22 2016-08-17 北京长信太和节能科技有限公司 Super clean endless integrated device of organic catalysis of coal fired boiler flue gas low temperature

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1698929A (en) * 2005-05-09 2005-11-23 中国科学院过程工程研究所 Functionalized ion liquid of alcoholamine carboxylate
US20140294718A1 (en) * 2013-03-29 2014-10-02 Korea Institute Of Science And Technology Novel sulfur dioxide and/or sulfur dioxide hydrate absorbent
CN205461713U (en) * 2016-03-22 2016-08-17 北京长信太和节能科技有限公司 Super clean endless integrated device of organic catalysis of coal fired boiler flue gas low temperature

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107198937A (en) * 2017-05-08 2017-09-26 西安热工研究院有限公司 A kind of method of wet process of FGD
CN109126417A (en) * 2018-08-01 2019-01-04 深圳前海中盛环保科技有限公司 The method of industrial smoke synchronized desulfuring and denitrifying
CN109126417B (en) * 2018-08-01 2020-07-07 深圳前海中盛环保科技有限公司 Synchronous desulfurization and denitrification method for industrial flue gas

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