CN103007752A - Wet-type reduction, denitration and harmless treatment method for smoke - Google Patents
Wet-type reduction, denitration and harmless treatment method for smoke Download PDFInfo
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- CN103007752A CN103007752A CN201210578309XA CN201210578309A CN103007752A CN 103007752 A CN103007752 A CN 103007752A CN 201210578309X A CN201210578309X A CN 201210578309XA CN 201210578309 A CN201210578309 A CN 201210578309A CN 103007752 A CN103007752 A CN 103007752A
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- flue gas
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Abstract
The invention relates to a wet-type reduction, denitration and harmless treatment method for smoke. The method comprises the following steps of: introducing the smoke containing NOX into an acid ferrous solution; absorbing the NOX at 0 to 100 DEG C to generate dark brown absorption liquid with nitroso-ferrous salt, nitric acid and nitrous acid so as to realize smoke denitration treatment; and finally, adding a reducing agent and a catalyst into the denitrated absorption liquid so as to convert absorbed nitroso groups into nitrogen. Therefore, the harmless treatment of the smoke can be realized.
Description
Technical field
The present invention relates to the flue gases purification field, particularly a kind of flue gas wet type reduction denitration and method for innocent treatment.
Background technology
Containing the harmful components nitrogen oxide in the gas that fuel combustion generates, wherein mainly is nitric oxide, nitrogen dioxide, and the dinitrogen pentoxide of nitrogen trioxide and trace, NO made in brief note
XEliminate NO
X, make the technical process of emission gases purification denitration.
At present, China is for the NO of burning generation
xDuring controlling, burn before mainly containing burning, control method controls three classes after control and the burning.Control refers to select low nitrogen fuel before the burning, but cost is very high, and engineering is used less.Control refers to improve combustion system and production technology in the burning, adopts low NOx combusting technology, reduces NO in the stove
xGrowing amount, the method expense is lower, but because the limitation of the interior low nitrogen burning technology of stove, so that NO
xThe control effect can not be satisfactory.Control refers at flue afterbody De-NO_x, with the NO in the flue gas after the burning
xChange harmless N into
2Or useful fertilizer.Because the NO of denitrating flue gas
xRemoval efficiency is high, and operation is simple, therefore, seeks technical advanced person, and the gas denitrifying technology of reasonable in economy is China control NO
xThe emphasis of discharging work.
Gas denitrifying technology mainly contains selective catalytic reduction (SCR), non-selective catalytic reduction (NSCR), SNCR method (SNCR), ozone oxidation absorption process, activated carbon combined desulfurization, denitration method etc.Because SCR method denitration efficiency is up to more than 90%, reliable, be present domestic and international application at most and one of the most ripe gas denitrifying technology.But the inventor's patent right of SCR gas denitrifying technology belongs to the U.S., and has cost high, and equipment investment is large, and operating cost is higher, the inferior positions such as the inadequate and easy poisoning of catalyst strength.
Therefore study a kind of high efficiency, operating cost is low, and resource consumption is few, configuration device and simple process, and the gas denitrifying technology of autonomous property right with novelty is significant.
Summary of the invention
The object of the invention is to provide a kind of high efficiency, and operating cost is low, and resource consumption is few, the reduction denitration of flue gas wet type and the method for innocent treatment of configuration device and simple process.
In order to solve the problems of the technologies described above, the invention provides a kind of flue gas wet type reduction denitration and method for innocent treatment, comprising: pending flue gas is passed in the acid ferrous iron solution, under 0-100 ℃ temperature conditions, absorb NO
XGenerate the mixed liquor of auburn nitroso-ferrous salt, nitric acid and nitrous acid, above-mentioned mixed solution is reduced processing, pending flue gas is reached clean discharging.
Further, pending flue gas is passed in the acid ferrous iron solution, under the temperature conditions of an atmospheric pressure, 0-100 ℃, the reaction time is 0-4h, absorbs NO
XGenerate the mixed liquor of auburn nitroso-ferrous salt, nitric acid and nitrous acid, above-mentioned mixed solution is reduced processing, pending flue gas is reached clean discharging.
Further, pending flue gas is passed in the acid ferrous iron solution, under 0-100 ℃ temperature conditions, the reaction time is 0-4h, absorbs NO
XGenerate the mixed liquor of auburn nitroso-ferrous salt, nitric acid and nitrous acid, above-mentioned mixed solution is reduced processing, pending flue gas is reached clean discharging.
Further, described flue gas comprises: all high temp. combustion of fuels produce contains NO
XGas.
Further, described acid ferrous iron solution comprises: frerrous chloride and/or ferrous sulfate, wherein the concentration of ferrous iron solution is controlled at 1-3mol/L in the solution.
Further, the initial hydrogen ion concentration is 0.6-1mol/L in the described acid ferrous iron solution.
Further, hydrogen ion concentration is 0.3-2mol/L in the described acid ferrous iron solution.
Further, described above-mentioned mixed solution is reduced to process comprise: will be in the mixed solution of above-mentioned nitroso-ferrous salt, nitric acid and nitrous acid adding reducing agent and catalyst, carry out reduction reaction, make nitroso change into nitrogen and emit, thereby realize cleaning discharging.
Further, the ferrous iron solution that generates of the described reduction reaction ferrous iron solution circulation that can be used as smoke treatment absorbs.
Further, described reducing agent comprises iron powder or sodium sulfite.
Further, described catalyst is Cu-Mn(I) or active carbon.
Further, when adopting iron powder to make reducing agent to carry out the absorption liquid post processing, hydrogen ion concentration is 0.6-1mol/L in the absorption liquid.
A kind of flue gas wet type reduction denitration provided by the invention and method for innocent treatment, the iron that is used for denitrification process is absorption liquid, can regenerate, can realize recycling, thereby reduce the operating cost of system.Nitrogen oxide in the flue gas finally reclaims as the nitrogen resource, really realizes energy-saving and emission-reduction, and recycling economy turns waste into wealth, and potential economic benefit is huge.The method is in processing procedure and recycling process, and non-secondary pollution is realized the innoxious of flue gas and clean discharging that environmental benefit is obvious.
Description of drawings
Fig. 1 is a kind of flue gas wet type reduction denitration that provides of the embodiment of the invention and the schematic flow sheet of method for innocent treatment.
The specific embodiment
Referring to Fig. 1, the present invention adopts the ferrous iron acid solution to do to contain NO
XThe absorption liquid of flue gas, wherein two valency ferrous solutions comprise: frerrous chloride and/or ferrous sulfate etc.; The kind of the acid in the acid medium comprises: hydrochloric acid and/or sulfuric acid.The concentration of ferrous iron solution is controlled at 1-3mol/L, and hydrogen ion concentration is 0.6-1mol/L in its acid medium, under 0-100 ℃ temperature conditions, absorbs NO
X, generate auburn nitroso-ferrous salt, the mixed liquor of nitric acid and nitrous acid.This mixed liquor can be processed by catalytic reduction method, makes it reach the innoxious purpose of cleaning, namely gets respectively the mixed solution of determining volume, adds a kind of of following reducing agent, and reducing agent comprises: iron powder or sodium sulfite etc.; Add a kind of of following catalyst, catalyst comprises: Cu-Mn(II) or active carbon etc.If wherein adopt iron powder to make reducing agent, absorption liquid must guarantee that hydrogen ion concentration is 0.6-1mol/L.Absorption liquid black takes off, and becomes gradually emerald two valency ferrous solutions, and the gas nitrogenfree oxide of release detects, and is mainly nitrogen, can directly enter air.The green ferrous iron solution reusable edible that this reaction generates.
Embodiment 1
Getting hydrogen ion concentration is 1mol/L, and ferrous iron concentration is the ferrous chloride solution 1L of 2.7mol/L, then in 30 ℃, under the atmospheric pressure, pass into nitric oxide gas, intake is 1.7mol, reaction time is 0-4h, become dark brown to absorption liquid and stop, leaving standstill 1h after, this absorption liquid adds 214g sodium sulfite solid and 5g activated-carbon catalyst, fully stir, the gas that discharges detects through gas detecting instrument, and main component is nitrogen, and nitrogenfree oxide detects.
Embodiment 2
Getting hydrogen ion concentration is 0.7mol/L, and ferrous iron concentration is the ferrous chloride solution 300ml of 1.3mol/L, then in 30 ℃, under the atmospheric pressure, pass into nitric oxide gas, intake is 0.39mol, reaction time is 0-3h, become dark brown to absorption liquid and stop, leaving standstill 1h after, this absorption liquid adds the sodium sulfite solid of 49g and the Cu-Mn(II of 5g) catalyst, fully stir, the gas that discharges detects through gas detecting instrument, and main component is nitrogen, and nitrogenfree oxide detects.
The present invention has the following effect of having a mind to:
1, changing existing treatment process, when realizing denitration, reduced cost of investment and unit scale, reduced operating cost, is an important breakthrough to gas denitrifying technology, has really realized social benefit, the organic unity of economic benefit and environmental benefit.
2, this technique has been opened the once technical revolution of denitration industry, has good future in engineering applications.Technological precedence belongs to domestic initiation, and will fill up international blank.Its Transformation Application will have far-reaching social value.
3, to be used for the iron of denitrification process be absorption liquid to this technology, can regenerate, can realize recycling, thereby reduce the operating cost of system.Nitrogen oxide in the flue gas finally reclaims as the nitrogen resource, really realizes energy-saving and emission-reduction, and recycling economy turns waste into wealth, and potential economic benefit is huge.
4, in the processing procedure and recycling process of this technology operation, non-secondary pollution is realized the innoxious of flue gas and cleans discharging that environmental benefit is obvious.
5, compare with existing denitration technology, have equipment and simplify, take up an area and lack, reduced investment, operating cost is low, and denitration efficiency is stable, and operation is simple and reliable, the characteristics of convenient management.
Claims (12)
1. flue gas wet type reduction denitration and method for innocent treatment is characterized in that, comprising:
Pending flue gas is passed in the acid ferrous iron solution, under 0-100 ℃ temperature conditions, absorb NO
XGenerate the mixed liquor of auburn nitroso-ferrous salt, nitric acid and nitrous acid, above-mentioned mixed solution is reduced processing, pending flue gas is reached clean discharging.
2. flue gas wet type reduction denitration according to claim 1 and method for innocent treatment is characterized in that,
Pending flue gas is passed in the acid ferrous iron solution, and under the temperature conditions of an atmospheric pressure, 0-100 ℃, the reaction time is 0-4h, absorbs NO
XGenerate the mixed liquor of auburn nitroso-ferrous salt, nitric acid and nitrous acid, above-mentioned mixed solution is reduced processing, pending flue gas is reached clean discharging.
3. flue gas wet type reduction denitration according to claim 1 and method for innocent treatment is characterized in that,
Pending flue gas is passed in the acid ferrous iron solution, and under 0-100 ℃ temperature conditions, the reaction time is 0-4h, absorbs NO
XGenerate the mixed liquor of auburn nitroso-ferrous salt, nitric acid and nitrous acid, above-mentioned mixed solution is reduced processing, pending flue gas is reached clean discharging.
4. according to claim 1-3 each reduction denitration of described flue gas wet type and method for innocent treatment is characterized in that described flue gas comprises:
All high temp. combustion of fuels produce contains NO
XGas.
5. according to claim 1-3 each reduction denitration of described flue gas wet type and method for innocent treatment is characterized in that described acid ferrous iron solution comprises:
Frerrous chloride and/or ferrous sulfate, wherein the concentration of ferrous iron solution is controlled at 1-3mol/L in the solution.
6. flue gas wet type according to claim 5 reduction denitration and method for innocent treatment is characterized in that:
The initial hydrogen ion concentration is 0.6-1mol/L in the described acid ferrous iron solution.
7. flue gas wet type according to claim 5 reduction denitration and method for innocent treatment is characterized in that:
Hydrogen ion concentration is 0.3-2mol/L in the described acid ferrous iron solution.
8. flue gas wet type according to claim 5 reduction denitration and method for innocent treatment is characterized in that, described above-mentioned mixed solution is reduced to process comprise:
With adding reducing agent and catalyst in the mixed solution of above-mentioned nitroso-ferrous salt, nitric acid and nitrous acid, carry out reduction reaction, make nitroso change into nitrogen and emit, thereby realize cleaning discharging.
9. flue gas wet type according to claim 8 reduction denitration and method for innocent treatment is characterized in that:
The ferrous iron solution circulation that the ferrous iron solution that described reduction reaction generates can be used as smoke treatment absorbs.
10. flue gas wet type reduction denitration according to claim 8 and method for innocent treatment is characterized in that described reducing agent comprises iron powder or sodium sulfite.
11. flue gas wet type reduction denitration according to claim 8 and method for innocent treatment is characterized in that:
Described catalyst is Cu-Mn(I) or active carbon.
12. flue gas wet type reduction denitration according to claim 8 and method for innocent treatment is characterized in that:
When adopting iron powder to make reducing agent to carry out the absorption liquid post processing, hydrogen ion concentration is 06-1mol/L in the absorption liquid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN201210578309.XA CN103007752B (en) | 2012-09-12 | 2012-12-27 | A kind of flue gas Wet-type reduction, denitration and method for innocent treatment |
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|---|---|---|---|
| CN2012103377373A CN102794099A (en) | 2012-09-12 | 2012-09-12 | Flue gas wet-type reduction denitration and harmless processing method |
| CN201210337737.3 | 2012-09-12 | ||
| CN201210578309.XA CN103007752B (en) | 2012-09-12 | 2012-12-27 | A kind of flue gas Wet-type reduction, denitration and method for innocent treatment |
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| CN103007752A true CN103007752A (en) | 2013-04-03 |
| CN103007752B CN103007752B (en) | 2016-01-06 |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1990089A (en) * | 2005-12-28 | 2007-07-04 | 浙江大学 | Wet process complex denitration technique enhancing Fe*EDTA by using sulfite reducing agent |
| CN101637688A (en) * | 2009-08-14 | 2010-02-03 | 暨南大学 | Treatment method and device for waste gas containing nitrogen oxides |
-
2012
- 2012-09-12 CN CN2012103377373A patent/CN102794099A/en not_active Withdrawn
- 2012-12-27 CN CN201210578309.XA patent/CN103007752B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1990089A (en) * | 2005-12-28 | 2007-07-04 | 浙江大学 | Wet process complex denitration technique enhancing Fe*EDTA by using sulfite reducing agent |
| CN101637688A (en) * | 2009-08-14 | 2010-02-03 | 暨南大学 | Treatment method and device for waste gas containing nitrogen oxides |
Non-Patent Citations (3)
| Title |
|---|
| > 20100630 王莉 湿法脱硝技术在燃煤烟气净化中的应用及研究进展 第74页 1-12 第10卷, 第3期 * |
| 张金龙: "湿法烟气脱硝技术研究进展", 《上海电力学院学报》 * |
| 王莉: "湿法脱硝技术在燃煤烟气净化中的应用及研究进展", <<安全与环境学报>> * |
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| CN103007752B (en) | 2016-01-06 |
| CN102794099A (en) | 2012-11-28 |
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