CN102989302A - Smoke wet oxidation denitration method - Google Patents
Smoke wet oxidation denitration method Download PDFInfo
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- CN102989302A CN102989302A CN2012105812798A CN201210581279A CN102989302A CN 102989302 A CN102989302 A CN 102989302A CN 2012105812798 A CN2012105812798 A CN 2012105812798A CN 201210581279 A CN201210581279 A CN 201210581279A CN 102989302 A CN102989302 A CN 102989302A
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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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- 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
- Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
- Y02C20/00—Capture or disposal of greenhouse gases
- Y02C20/10—Capture or disposal of greenhouse gases of nitrous oxide (N2O)
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Abstract
The invention relates to a smoke wet oxidation denitration method which comprises leading NOX contained smoke to be processed in an acidity ferrous solution, absorbing the NOX, generating puce mixed liquor of nitrous ferrite salt, nitric acid and nitrous acid after ferrous ion is combined with nitric oxide immediately, and then conducting oxidation desorbing treatment on the mixed liquor. The denitration absorption liquid is added in an oxidizing agent to release nitrogen dioxide which is dissolved in a water solution, an ammonia water solution, a potassium hydroxide solution or a sodium hydroxide solution to generate nitric acid, ammonium nitrate, potassium nitrate, sodium nitrate and the like, and accordingly resource utilization is achieved.
Description
Technical field
The present invention relates to the purification techniques field of flue gas, particularly a kind of fume wet-type method of denitration.
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, the NOx control method that produces for burning of China mainly contains in control before the burning, the burning control three classes after the control and burning.Control refers to select low nitrogen fuel before the burning, but cost is very high, and engineering is used less.Control in the burning and refer to improve combustion system and production technology, adopt low NOx combusting technology, reduce NOx growing amount in the stove, the method expense is lower, but because the limitation of the interior low nitrogen burning technology of stove, so that the control effect of NOx can not be satisfactory.Control refers to change the NOx in the flue gas into harmless N2 or useful fertilizer at flue afterbody De-NO_x after the burning.Because the NOx removal efficiency of denitrating flue gas is high, operation is simple, therefore, seeks technical advanced person, and the gas denitrifying technology of reasonable in economy is the emphasis of China control NOx 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 fume wet-type method of denitration.
The invention provides a kind of fume wet-type method of denitration, will contain NO
XPending flue gas pass in the acid ferrous iron solution, absorb NO
X, ferrous ion is combined the mixed liquor that generates auburn nitroso-ferrous salt, nitric acid and nitrous acid immediately with nitric oxide, then this mixed liquor is carried out the oxidation desorb and process.
Further, will contain NO
XPending flue gas pass in the acid ferrous iron solution, under the temperature conditions of an atmospheric pressure, 0-100 ℃, reaction 0-4h absorbs NO
XFerrous ion is combined the mixed liquor that generates auburn nitroso-ferrous salt, nitric acid and nitrous acid immediately with nitric oxide, then this mixed liquor is added oxidant and carry out oxidation desorb processing, in desorption process, ferrous iron is oxidized to ferric iron and emits nitric oxide, and nitric oxide is oxidized to again nitrogen dioxide immediately simultaneously.
Further, will contain NO
XPending flue gas pass in the acid ferrous iron solution, under 0-100 ℃ temperature conditions, reaction 0-4h absorbs NO
XFerrous ion is combined the mixed liquor that generates auburn nitroso-ferrous salt, nitric acid and nitrous acid immediately with nitric oxide, then this mixed liquor is added oxidant and carry out oxidation desorb processing, in desorption process, ferrous iron is oxidized to ferric iron and emits nitric oxide, and nitric oxide is oxidized to again nitrogen dioxide immediately simultaneously.The NO that discharges
2Gas obtains different product through liquid absorption, makes flue gas reach the recycling purpose.
Further, comprise that also stripping liquid that oxidation processes desorb gained contains ferric ion adds reducing agent and processes, the absorption liquid that contains ferrous ion of generation enters next circulation absorption process.
Further, the nitrogen dioxide of emitting is collected and safe storage.
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 flue gas reaches recycling and comprises: the NO that described oxidation reaction discharges
2Gas is absorbed by water, ammoniacal liquor, potassium hydroxide or sodium hydroxide solution, the NO that discharges
2Gas is absorbed the NO that reclaims nitric acid, discharges by water
2The NO that gas is reclaimed ammonium nitrate, discharges by ammonia absorption
2Gas is absorbed the NO that reclaims potassium nitrate, discharges by potassium hydroxide solution
2Gas is absorbed by sodium hydroxide solution and reclaims sodium nitrate.
Further, described oxidant comprises oxygen or ozone.
Further, described reducing agent comprises iron powder or ferrous sulfide.
A kind of fume wet-type method of denitration provided by the invention when realizing denitration, finally reclaims the nitrogen oxide in the flue gas as the nitrogen resource, really realize energy-saving and emission-reduction, and recycling economy turns waste into wealth, and potential economic benefit is huge.
Description of drawings
Fig. 1 is a kind of fume wet-type method of denitration schematic flow sheet that the embodiment of the invention provides.
The specific embodiment
Referring to shown in Figure 1, the present invention adopts the ferrous iron acid solution to do to contain NO
XThe absorption liquid of flue gas, 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, ferrous ion is combined with nitric oxide immediately and is generated auburn nitroso-ferrous salt, the mixed liquor of nitric acid and nitrous acid.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 auburn nitroso-ferrous salt of above-mentioned gained, the mixed liquor of nitric acid and nitrous acid can pass through oxidative treatment, achieves resource and innoxious.Get respectively the absorption mixed liquor of determining volume, pass into or add a kind of of following oxidant, oxidant comprises: oxygen or ozone etc.Ferrous iron is oxidized to trivalent in the absorption liquid, and the nitric oxide that discharges simultaneously is oxidized to nitrogen dioxide immediately, and wherein large then enters in the suitable absorption liquid and be absorbed, and generates corresponding chemical products.The stripping liquid of ferric ion adds reducing agent to be processed, and generates the absorption liquid that contains ferrous ion and enters next circulation absorption process; After the recycled for multiple times, smoke absorption liquid separates, purifying, and crystallization gets ferric nitrate or iron chloride product.
NO
2Suitable absorption liquid comprise: water, ammoniacal liquor, potassium hydroxide solution, sodium hydroxide solution etc.Do the recyclable nitric acid of absorption liquid with water; The recyclable ammonium nitrate take ammoniacal liquor as absorption liquid, with potassium hydroxide, the solution such as NaOH are done the recyclable potassium nitrate of absorption liquid, sodium nitrate etc.
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, and the reaction time is 0-4h, becoming dark brown to absorption liquid stops, after leaving standstill 1h, this absorption liquid passes into oxygen 1.35mol, and the reaction time is 3-5h, the nitrogen dioxide gas that discharges is absorbed by 1L distilled water, to the residue gas of emitting without till the nitrogen dioxide.Record that contained concentration of nitric acid is 0.77mol/L in the absorption liquid.
Embodiment 2
The flue gas that certain near coal-mine power plant discharges is drawn a part, and passing into hydrogen ion concentration is 1mol/L, and concentration is in the ferrous iron solution of 1.8mol/L, under 70 ℃, absorbs NO
XGenerate the mixed liquor of auburn nitroso-ferrous salt, nitric acid and nitrous acid, after 1 year, get denitration and process gained mixed liquor 5L, pass into excessive oxygen, the nitrogen dioxide that blows out absorbs through the water one-level and makes the dilute nitric acid solution 200ml that concentration is 0.1mol/L.This shows that temperature is high, and the time is long, and assimilation effect and resource effect can reduce.
Embodiment 3
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, and the reaction time is 0-3h, becoming dark brown to absorption liquid stops, after leaving standstill 1h, this absorption liquid passes into oxygen 0.22mol, and the reaction time is 0-5h, the nitrogen dioxide gas that discharges is absorbed by 500ml distilled water, to the residue gas of emitting without till the nitrogen dioxide.Record that contained concentration of nitric acid is 0.48mol/L in the absorption liquid.
A kind of fume wet-type method of denitration provided by the invention has following beneficial effect:
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, the present invention has 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.
It should be noted last that, the above specific embodiment is only unrestricted in order to technical scheme of the present invention to be described, although with reference to example the present invention is had been described in detail, those of ordinary skill in the art is to be understood that, can make amendment or be equal to replacement technical scheme of the present invention, and not breaking away from the spirit and scope of technical solution of the present invention, it all should be encompassed in the middle of the claim scope of the present invention.
Claims (12)
1. fume wet-type method of denitration is characterized in that:
To contain NO
XPending flue gas pass in the acid ferrous iron solution, absorb NO
X, ferrous ion is combined the mixed liquor that generates auburn nitroso-ferrous salt, nitric acid and nitrous acid immediately with nitric oxide, then this mixed liquor is carried out the oxidation desorb and process.
2. method according to claim 1 is characterized in that,
To contain NO
XPending flue gas pass in the acid ferrous iron solution, under the temperature conditions of an atmospheric pressure, 0-100 ℃, reaction 0-4h absorbs NO
XFerrous ion is combined the mixed liquor that generates auburn nitroso-ferrous salt, nitric acid and nitrous acid immediately with nitric oxide, then this mixed liquor is added oxidant and carry out oxidation desorb processing, in desorption process, ferrous iron is oxidized to ferric iron and emits nitric oxide, and nitric oxide is oxidized to again nitrogen dioxide immediately simultaneously.
3. method according to claim 1 is characterized in that,
To contain NO
XPending flue gas pass in the acid ferrous iron solution, under 0-100 ℃ temperature conditions, reaction 0-4h absorbs NO
XFerrous ion is combined the mixed liquor that generates auburn nitroso-ferrous salt, nitric acid and nitrous acid immediately with nitric oxide, then this mixed liquor is added oxidant and carry out oxidation desorb processing, in desorption process, ferrous iron is oxidized to ferric iron and emits nitric oxide, and nitric oxide is oxidized to again nitrogen dioxide immediately simultaneously.
4. each described method is characterized in that according to claim 1-3, also comprises:
The stripping liquid that gained contains ferric ion after the oxidation desorb is processed adds reducing agent to be processed, and the absorption liquid that contains ferrous ion of generation enters next circulation absorption process.
5. each described method according to claim 1-3 is characterized in that:
The nitrogen dioxide of emitting is collected and safe storage.
6. each described method according to claim 1-3 is characterized in that:
Described flue gas comprises: all high temp. combustion of fuels produce contains NO
XGas.
7. each described method according to claim 1-3 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.
8. each described method according to claim 1-3 is characterized in that:
The initial hydrogen ion concentration is 0.6-1mol/L in the described acid ferrous iron solution.
9. each described method according to claim 1-3 is characterized in that:
Hydrogen ion concentration is 0.3-2mol/L in the described acid ferrous iron solution.
10. method according to claim 4 is characterized in that, described flue gas reaches recycling and comprises:
The NO that described oxidation reaction discharges
2Gas is absorbed by water, ammoniacal liquor, potassium hydroxide or sodium hydroxide solution, the NO that discharges
2Gas is absorbed the NO that reclaims nitric acid, discharges by water
2The NO that gas is reclaimed ammonium nitrate, discharges by ammonia absorption
2Gas is absorbed the NO that reclaims potassium nitrate, discharges by potassium hydroxide solution
2Gas is absorbed by sodium hydroxide solution and reclaims sodium nitrate.
11. according to claim 2 or 3 described methods, it is characterized in that:
Described oxidant comprises oxygen or ozone.
12. method according to claim 4 is characterized in that:
Described reducing agent comprises iron powder or ferrous sulfide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012105812798A CN102989302A (en) | 2012-09-12 | 2012-12-27 | Smoke wet oxidation denitration method |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012103377369A CN102794098A (en) | 2012-09-12 | 2012-09-12 | Flue gas wet-type oxidation denitration and resource utilization method |
| CN201210337736.9 | 2012-09-12 | ||
| CN2012105812798A CN102989302A (en) | 2012-09-12 | 2012-12-27 | Smoke wet oxidation denitration method |
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| CN102989302A true CN102989302A (en) | 2013-03-27 |
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| CN2012103377369A Withdrawn CN102794098A (en) | 2012-09-12 | 2012-09-12 | Flue gas wet-type oxidation denitration and resource utilization method |
| CN201210580919.3A Expired - Fee Related CN103007725B (en) | 2012-09-12 | 2012-12-27 | Wet-type oxidative denitration and energy utilization method of smoke |
| CN2012105812798A Pending CN102989302A (en) | 2012-09-12 | 2012-12-27 | Smoke wet oxidation denitration method |
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| CN2012103377369A Withdrawn CN102794098A (en) | 2012-09-12 | 2012-09-12 | Flue gas wet-type oxidation denitration and resource utilization method |
| CN201210580919.3A Expired - Fee Related CN103007725B (en) | 2012-09-12 | 2012-12-27 | Wet-type oxidative denitration and energy utilization method of smoke |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107638801A (en) * | 2017-10-30 | 2018-01-30 | 江苏科行环保科技有限公司 | The low emission technique and complexes of pollutant in garbage power generation boiler flue gas |
| CN114682067A (en) * | 2020-12-26 | 2022-07-01 | 黄华丽 | Device and process for removing nitric oxide in airflow |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102794098A (en) * | 2012-09-12 | 2012-11-28 | 河南绿典环保节能科技有限公司 | Flue gas wet-type oxidation denitration and resource utilization method |
| CN103239981A (en) * | 2013-05-14 | 2013-08-14 | 成都信息工程学院 | Method for denitrating flue gas by ferrous-citrate-iron powder mixed-liquid wet process and by-producing ammonium nitrate |
| CN107398165B (en) * | 2017-08-10 | 2020-10-20 | 上海博丹环境工程技术股份有限公司 | Desulfurization and denitrification process for boiler flue gas |
| CN111167263B (en) | 2018-11-13 | 2021-04-13 | 黄华丽 | Nitrogen oxide absorbent slurry and preparation and use methods thereof |
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- 2012-09-12 CN CN2012103377369A patent/CN102794098A/en not_active Withdrawn
- 2012-12-27 CN CN201210580919.3A patent/CN103007725B/en not_active Expired - Fee Related
- 2012-12-27 CN CN2012105812798A patent/CN102989302A/en active Pending
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| CN114682067A (en) * | 2020-12-26 | 2022-07-01 | 黄华丽 | Device and process for removing nitric oxide in airflow |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103007725A (en) | 2013-04-03 |
| CN103007725B (en) | 2015-03-18 |
| CN102794098A (en) | 2012-11-28 |
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Application publication date: 20130327 |