CN104084025A - Method for removing nitric oxides from boiler smoke - Google Patents
Method for removing nitric oxides from boiler smoke Download PDFInfo
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- CN104084025A CN104084025A CN201410341575.XA CN201410341575A CN104084025A CN 104084025 A CN104084025 A CN 104084025A CN 201410341575 A CN201410341575 A CN 201410341575A CN 104084025 A CN104084025 A CN 104084025A
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- edta
- boiler smoke
- iron
- nitrogen oxide
- smoke removal
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Abstract
The invention discloses a method for removing nitric oxides from boiler smoke. The method comprises the following steps of firstly introducing smoke into a Fe<II>EDTA solution, complexing and absorbing NO to obtain a ferrous acyl complex Fe<II>(NO)EDTA, introducing Fe<II>(NO)EDTA into a regenerating device, and reducing Fe<II>(NO)EDTA by virtue of metallic iron so as to regenerate Fe<II>EDTA and converting NO into high-concentration NH3 simultaneously. The method has the beneficial effects that by removing NO in smoke by virtue of a liquid-phase complexing absorbent, the technical problem that NO is difficult to enter a liquid phase is effectively solved; the absorption and the regeneration are separately carried out, so that the concentration of NH3 is increased, and the problem that an NH3 absorbing device is too large can be solved; generated NH3 can generate ammonium salt which can be taken as an industrial raw material or a reducing agent to enter other SNCR denitration reactors for boiler smoke, and hydrous precipitates of ferric oxide generated from iron can be taken as chemical products such as iron oxide red pigments.
Description
Technical field
The present invention relates to a kind of method of gas cleaning, relate in particular to a kind of method of boiler smoke removal of nitrogen oxide.
Background technology
In industrial waste gas, mainly contain NO and NO
2, and the concentration of NO is conventionally all far away higher than NO
2, particularly, in the NOx of combustion product gases, NO accounts for 95% left and right, NO
2the ratio accounting for is less.NO gas-liquid mass transferring resistance is large simultaneously, and in water, solubility is lower, and its processing procedure is very difficult.The discharge capacity of the current NOx of China, with the speed increase year after year up to 10%, expects the year two thousand twenty and will reach (2660～2970) × 104t, therefore carries out the pollution control research of NOx in atmosphere extremely urgent.
At present, NOx groundwater pollution control mainly contains three kinds: fuel denitride technology, low NOx combusting technology and gas denitrifying technology.But due to many-sided reason, fuel denitride technology and NOx combustion technology not yet reach comprehensive practical stage, denitrating flue gas remains NOx and pollutes the topmost method of controlling.
Most popular two classes that are divided into of gas denitrifying technology: selective catalytic reduction (SCR) and SNCR method (SNCR), their reaction mechanism is all taking ammonia as reducing agent, NOx in flue gas to be reduced into harmless nitrogen G&W, both main difference are that SCR uses catalyst, reaction temperature is lower, and SNCR does not use catalyst reaction temperatures higher.But these two kinds of methods all exist certain defect, and SCR method is higher to designing requirement, manufacture and operating cost are higher.In denitrification process, owing to containing SO in flue gas
2, water smoke and grit etc., can cause catalyst " poisoning " etc. to be unfavorable for the phenomenon of catalytic reaction.SNCR method ammonia consumption is high, and amount of ammonia slip is larger, and the difficulty mixing is large, so its denitration rate can only reach 50～60%.Emptyingly after the urea that simultaneously these two kinds of methods are use or ammonia incomplete reaction be easy to cause secondary pollution.
In recent years, adopt the wet denitration technical research of liquid complexing absorbing and removing nitrogen oxides in effluent extensively to carry out.The method utilizes liquid complexing agent directly to react with the NO that is insoluble in water in flue gas, makes NO enter liquid phase, thereby reaches the object of denitrating flue gas.According to the just research to liquid complexing absorption process of lot of domestic and foreign scholar, Fe
iIeDTA solution is to the extraordinary effect of being absorbed with of NO.But up to the present, liquid complexing method but is still difficult to realize industrialization, and its main cause is the Fe needing in denitrification process
iIeDTA consumption is larger, and price is higher, can increase process operation cost, simultaneously Fe
iIeDTA is easily oxidized to Fe that can not complexing NO in course of reaction
iIIeDTA, thus the denitration efficiency of technique can be reduced.There is afterwards scholar to propose with the living things catalysis reducing process Fe that regenerates
iIeDTA, but this method implementation process complexity, drop into practical application and also have a lot of problems to need to solve.Ma Lefan proposes with ferrous chelating agent complexed absorption NO, then reacts reducing/regenerating Fe by iron powder with the ferrous nitrosyl complex of generation
iIeDTA, its process using Integrated Architecture, complexed absorption and reducing/regenerating are in same reactor.The defect of this technique is the NH that reaction generates
3concentration is lower, and required NH
3the capacity of absorption plant must be equal to NO complexing device, and required like this equipment investment can increase greatly, can increase the difficulty of whole technological process operation simultaneously.
Summary of the invention
In order to solve the problems of the technologies described above, the invention provides a kind of method of boiler smoke removal of nitrogen oxide.
The technical scheme that the present invention solves the problems of the technologies described above is:
A method for boiler smoke removal of nitrogen oxide, comprises the steps:
(1) in absorber, with Fe
iIeDTA solution, as absorption liquid, reacts by complexed absorption, and in absorption flue gas, the utmost point is insoluble in the NO of water, the sub-acyl complex compound introducing of the ferrous iron generating after reaction reducing/regenerating device;
(2), in reducing/regenerating device, metallic iron and ferrous nitrosyl complex generation reduction reaction, be reduced to the NO in complex compound the NH of high concentration
3, Fe regenerates simultaneously
iIeDTA is cycled to used in and absorbs NO.
The method of above-mentioned boiler smoke removal of nitrogen oxide, described complexed absorption reaction temperature is 293K～323K, pH is 5.0～6.5, Fe
iIthe concentration of EDTA solution is 15～40mmol/L.
The method of above-mentioned boiler smoke removal of nitrogen oxide, described reduction reaction temperature is 293K～323K, described ferrous nitrosyl complex sprays on metallic iron, sprinkle density 0.2～1.0m
3/ (m
2h).
The method of above-mentioned boiler smoke removal of nitrogen oxide, described absorber is sieve-plate tower, rotating stream tray scrubber, spray column or bubble tower.
The method of above-mentioned boiler smoke removal of nitrogen oxide, described reducing/regenerating device is iron filings packed bed or iron powder stirred tank.
The method of above-mentioned boiler smoke removal of nitrogen oxide, described metallic iron is iron powder or iron filings.
Concrete course of reaction is as follows:
Flue gas passes in absorption liquid, Fe
iInO in EDTA complexed absorption flue gas:
Fe
ⅡEDTA+NO→Fe
Ⅱ(NO)EDTA
Iron powder reacts with ferrous nitrosyl complex, makes NO be reduced to NH
3, realize Fe simultaneously
iIeDTA reducing/regenerating:
2Fe
Ⅱ(NO)EDTA+Fe+8H+→2Fe
ⅡEDTA+Fe(OH)
2+2NH
3
NH
3in acid solution, can generate ammonium salt:
NH
3+H
+→NH
4 +
In the time there is oxygen in flue gas, can be by Fe
iIeDTA is oxidized to Fe
iIIeDTA and lose complexing, the existence of iron powder can address this problem:
Fe
ⅡEDTA+O
2→Fe
ⅢEDTA
Fe+Fe
3+→Fe
2+
The meeting of reacted iron powder in solution forms Fe (OH)
2hydrate, can generate Fe under certain condition
2o
3as iron oxide red raw material:
Fe(OH)
2→Fe
2O
3+H
2O。
Beneficial effect of the present invention is:
(1) the present invention adopts liquid complexing method, removes the NO in flue gas with liquid complexing absorbent, efficiently solves the technical difficulty that NO is difficult to enter liquid phase.
(2) complexed absorption reaction of the present invention and reducing/regenerating reaction are separately carried out in different device, and the ferrous nitrosyl complex that complexed absorption reaction generates is introduced separately into reducing/regenerating device, can solve NH
3the problem that absorption plant is too huge.
(3) the present invention's complexes absorption used can recycling, and reacted product can comprehensively utilize again, can not produce secondary pollution, and technological operation is simple, and denitration efficiency is high, is easy to industrialization.
(4) process product of the present invention has good value, the NH of generation
3pass in acid solution and can generate ammonium salt as the raw material of industry, also can be used as reducing agent and enter in SNCR Benitration reactor, the iron that reaction consumes can form the hydrate precipitate of iron oxide in solution, can be used as other chemical products such as iron oxide red pigment.
Brief description of the drawings
Fig. 1 is FB(flow block) of the present invention.
Fig. 2 is experimental provision of the present invention and schematic flow sheet: 1, air inlet, 2, absorption tower, 3, absorption cycle groove, 4, regeneration reactor, 5, dehydrator, 6, gas outlet.
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention is described in further details, but the present invention is not limited to this.
Embodiment 1
Fe
iInO in EDTA complexed absorption simulated flue gas: using the sieve plate absorber of diameter 100mm, high 1200mm as absorber, built-in 2 layers of sieve plate, percent opening 17%.Simulation NO exhaust gas flow 20m
3/ h, containing NO500 × 10
-6, absorption liquid Fe
iIeDTA concentration is 25mmolL
-1, internal circulating load is 80L/h, reaction temperature 323K, and the initial pH of complex liquid is that 5.5, NO removal efficiency is 97%.Regenerating unit is with the iron filings packed-bed reactor of diameter 200mm, high 400mm, sprinkle density 0.2m
3/ (m
2h), 5% the ammonia sulfuric acid absorption bearing again when 313K obtains ammonium sulfate, then the Fe bearing
iIeDTA solution circulation is for absorbing, and denitration efficiency is still in 97% left and right.
Embodiment 2
Fe
iInO in EDTA complexed absorption simulated flue gas: using the sieve plate absorber of diameter 100mm, high 1200mm as absorber, built-in 2 layers of sieve plate, percent opening 17%.Simulation NO exhaust gas flow 20m
3/ h, containing NO400 × 10
-6, absorption liquid Fe
iIeDTA concentration is 25mmolL
-1, internal circulating load is 80L/h, reaction temperature 323K, and the initial pH of complex liquid is that 5.5, NO removal efficiency is 98%.Regenerating unit is with the iron filings packed-bed reactor of diameter 200mm, high 400mm, sprinkle density 0.4m
3/ (m
2h), 5% the ammonia sulfuric acid absorption bearing again when 303K obtains ammonium sulfate, then the Fe bearing
iIeDTA solution circulation is for absorbing, and denitration efficiency is still in 98% left and right.
Embodiment 3
Fe
iInO in EDTA complexed absorption simulated flue gas: using the sieve plate absorber of diameter 100mm, high 1200mm as absorber, built-in 2 layers of sieve plate, percent opening 17%.Simulation NO exhaust gas flow 20m
3/ h, containing NO500 × 10
-6, absorption liquid Fe
iIeDTA concentration is 30mmolL
-1, internal circulating load is 100L/h, reaction temperature 323K, and the initial pH of complex liquid is that 6.0, NO removal efficiency is more than 97%.Regenerating unit is with the iron filings packed-bed reactor of diameter 200mm, high 400mm, sprinkle density 0.6m
3/ (m
2h), 5% the ammonia sulfuric acid absorption bearing again when 293K obtains ammonium sulfate, then the Fe bearing
iIeDTA solution circulation is for absorbing, and denitration efficiency is still in 96% left and right.
Embodiment 4
Fe
iInO in EDTA complexed absorption simulated flue gas: using the sieve plate absorber of diameter 100mm, high 1200mm as absorber, built-in 2 layers of sieve plate, percent opening 17%.Simulation NO exhaust gas flow 20m
3/ h, containing NO500 × 10
-6, absorption liquid Fe
iIeDTA concentration is 20mmolL
-1, internal circulating load is 60L/h, reaction temperature 313K, and the initial pH of complex liquid is that 6.0, NO removal efficiency is 98%.Regenerating unit is with the iron powder stirred tank reactor of diameter 200mm, high 400mm, 60 revs/min of speeds of agitator, and 5% the ammonia sulfuric acid absorption bearing again when 293K obtains ammonium sulfate, then the Fe bearing
iIeDTA solution circulation is for absorbing, and denitration efficiency is still in 97% left and right.
Embodiment 5
Fe
iInO in EDTA complexed absorption simulated flue gas: using the sieve plate absorber of diameter 100mm, high 1200mm as absorber, built-in 2 layers of sieve plate, percent opening 17%.Simulation NO exhaust gas flow 20m
3/ h, containing NO500 × 10
-6, absorption liquid Fe
iIeDTA concentration is 20mmolL
-1, internal circulating load is 60L/h, reaction temperature 323K, and the initial pH of complex liquid is that 5.5, NO removal efficiency is 98%.Regenerating unit is with the iron powder stirred tank reactor of diameter 200mm, high 400mm, 80 revs/min of speeds of agitator, and 5% the ammonia sulfuric acid absorption bearing again when 313K obtains ammonium sulfate, then the Fe bearing
iIeDTA solution circulation is for absorbing, and denitration efficiency is still in 97% left and right.
Claims (7)
1. a method for boiler smoke removal of nitrogen oxide, comprises the steps:
(1) in absorber, with Fe
iIeDTA solution, as absorption liquid, reacts by complexed absorption, and in absorption flue gas, the utmost point is insoluble in the NO of water, the sub-acyl complex compound introducing of the ferrous iron generating after reaction reducing/regenerating device;
(2), in reducing/regenerating device, metallic iron and ferrous nitrosyl complex generation reduction reaction, be reduced to the NO in complex compound the NH of high concentration
3, Fe regenerates simultaneously
iIeDTA is cycled to used in and absorbs NO.
2. the method for boiler smoke removal of nitrogen oxide according to claim 1, described complexed absorption reaction temperature is 293K～323K, pH is 5.0～6.5, Fe
iIthe concentration of EDTA solution is 15～40mmol/L.
3. the method for boiler smoke removal of nitrogen oxide according to claim 1, described reduction reaction temperature is 293K～323K.
4. according to the method for the boiler smoke removal of nitrogen oxide described in claim 1 or 3, described ferrous nitrosyl complex sprays on metallic iron, and sprinkle density is 0.2～1.0m
3/ (m
2h).
5. the method for boiler smoke removal of nitrogen oxide according to claim 1, described absorber is sieve-plate tower, rotating stream tray scrubber, spray column or bubble tower.
6. the method for boiler smoke removal of nitrogen oxide according to claim 1, described reducing/regenerating device is iron filings packed bed or iron powder stirred tank.
7. the method for boiler smoke removal of nitrogen oxide according to claim 1, described metallic iron is iron powder or iron filings.
Priority Applications (1)
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| CN201410341575.XA CN104084025B (en) | 2014-07-17 | 2014-07-17 | A kind of method of boiler smoke removal of nitrogen oxide |
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|---|---|---|---|
| CN201410341575.XA CN104084025B (en) | 2014-07-17 | 2014-07-17 | A kind of method of boiler smoke removal of nitrogen oxide |
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| Publication Number | Publication Date |
|---|---|
| CN104084025A true CN104084025A (en) | 2014-10-08 |
| CN104084025B CN104084025B (en) | 2016-04-20 |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107983133A (en) * | 2017-12-26 | 2018-05-04 | 上海亨远船舶设备有限公司 | A kind of system and method for flue gas wet type combined desulfurization and denitration |
| CN108854461A (en) * | 2018-05-24 | 2018-11-23 | 浙江工业大学 | Mn cooperates with Fe as reducing agentII(EDTA) application of resource processing NO |
| CN112717668A (en) * | 2020-12-11 | 2021-04-30 | 攀钢集团攀枝花钢铁研究院有限公司 | Efficient and stable complexing denitration agent and preparation method thereof |
| CN114682067A (en) * | 2020-12-26 | 2022-07-01 | 黄华丽 | Device and process for removing nitric oxide in airflow |
| CN115738599A (en) * | 2022-11-23 | 2023-03-07 | 攀钢集团攀枝花钢铁研究院有限公司 | Simultaneous absorption of NO x And preparation method of CO complexing denitration liquid |
Citations (4)
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| US4079118A (en) * | 1973-12-27 | 1978-03-14 | Chisso Engineering Co Ltd | Method for removing nitrogen oxides using ferricion-EDTA complex solutions |
| CN1546210A (en) * | 2003-12-15 | 2004-11-17 | 湘潭大学 | Method for removing nitric oxide from waste gas |
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2014
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Patent Citations (4)
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| US4079118A (en) * | 1973-12-27 | 1978-03-14 | Chisso Engineering Co Ltd | Method for removing nitrogen oxides using ferricion-EDTA complex solutions |
| CN1546210A (en) * | 2003-12-15 | 2004-11-17 | 湘潭大学 | Method for removing nitric oxide from waste gas |
| CN101306308A (en) * | 2008-01-23 | 2008-11-19 | 华东理工大学 | Method for synchronously treating the combined pollution exhaust gas containing nitric oxide and sulfur dioxide |
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Non-Patent Citations (1)
| Title |
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| 马乐凡 等: "Fe2+EDTA液相对NO的络合作用", 《生态环境》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107983133A (en) * | 2017-12-26 | 2018-05-04 | 上海亨远船舶设备有限公司 | A kind of system and method for flue gas wet type combined desulfurization and denitration |
| CN108854461A (en) * | 2018-05-24 | 2018-11-23 | 浙江工业大学 | Mn cooperates with Fe as reducing agentII(EDTA) application of resource processing NO |
| CN112717668A (en) * | 2020-12-11 | 2021-04-30 | 攀钢集团攀枝花钢铁研究院有限公司 | Efficient and stable complexing denitration agent and preparation method thereof |
| CN114682067A (en) * | 2020-12-26 | 2022-07-01 | 黄华丽 | Device and process for removing nitric oxide in airflow |
| CN115738599A (en) * | 2022-11-23 | 2023-03-07 | 攀钢集团攀枝花钢铁研究院有限公司 | Simultaneous absorption of NO x And preparation method of CO complexing denitration liquid |
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|---|---|
| CN104084025B (en) | 2016-04-20 |
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