CN104971594A - Gas phase oxidization-liquid phase oxidization-absorption three-section type dry-wet-process flue gas denitration process - Google Patents
Gas phase oxidization-liquid phase oxidization-absorption three-section type dry-wet-process flue gas denitration process Download PDFInfo
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Abstract
The invention discloses a gas phase oxidization-liquid phase oxidization-absorption three-section type dry-wet-process flue gas denitration process. According to the process, ozone is used as a gas-phase oxidant to oxidize one part of nitric oxide in flue gas into high-valence-state nitric oxide capable of being absorbed by slurry; any one or a mixture solution of more of hydrogen peroxide, sodium hypochlorite, sodium chlorite, sodium chlorate, sodium persulfate, potassium chlorate, potassium hypermanganate and potassium dichromate is sprayed to be used as a liquid-phase oxidant to oxidize the residual high-valence-state nitric oxide in the flue gas into the high-valence-state nitric oxide; and the flue gas enters an absorption tower and a magnesium hydroxide solution is sprayed to absorb the high-valence-state nitric oxide. Compared with the prior art, the process firstly adopts two times of oxidization of a gas phase and a liquid phase and a magnesium oxide wet process is used for absorbing so that a target of efficiently removing the nitric oxide is realized; and by virtue of the technical scheme, the use amount of the ozone is reduced, the equipment cost and operation cost are reduced and the denitration efficiency is improved and can reach more than or equal to 93%.
Description
Technical field
The present invention relates to gas cleaning processing technology field, be specifically related to a kind of gaseous oxidation-liquid phase oxidation-absorption syllogic wet-dry change flue-gas denitration process.
Background technology
The selective catalytic reduction of denitration technology (SCR) of domestic contrast maturation and SNCR (SNCR) two kinds.
SCR denitration technology refers under catalyst action and under uniform temperature, reacting with reducing agent and generating nitrogen and water of the nitrous oxides selectivity in flue gas, reaches the object removing nitrogen oxide.In SCR denitration technology, catalyst costs is expensive, accounts for 40 ~ 60% of whole denitrating system device total cost.And there is the catalyst easily problem such as poisoning, blocking.How to keep the activity of catalyst, increase the service life also being that SCR denitration system needs to solve part.
Under the denitration of SNCR method refers to the effect of catalyst-free, in " temperature window " of applicable denitration reaction, spraying into reducing agent by the reduction of nitrogen oxide in flue gas is harmless nitrogen and water.This technology generally adopts in stove sprays ammonia, urea or hydrogen propylhomoserin as reducing agent reducing NOx.The NOx reaction of reducing agent only and in flue gas, generally do not react with oxygen, this technology does not adopt catalyst, is in this way called as SNCR method (SNCR), but the denitration efficiency of SNCR is not very high, only has about 50%.
Therefore, the research and development of a kind of low equipment cost, low operating cost, high efficiency gas denitrifying technology are problems that is very valuable and technical prospect.
Summary of the invention
The object of the invention is to overcome above-mentioned defect, ozone is first adopted to be the high-valence state nitrogen oxide that can be absorbed by slurries as gaseous oxidizing agent by part oxidation of nitric oxide in flue gas, spray the nitric oxide of any one or a few the mixed solution in hydrogen peroxide, clorox, sodium chlorite, sodium chlorate, sodium peroxydisulfate, potassium chlorate, potassium permanganate, potassium bichromate as remnants in Oxygen in Liquid agent oxidation flue gas again, flue gas sprays magnesium hydroxide solution by the nox adsorption of high-valence state after entering absorption tower.Realize the target of efficient removal nitrogen oxide, decrease the use amount of ozone, reduce equipment cost and operating cost, improve denitration efficiency.
The technical solution used in the present invention is as follows:
A kind of gaseous oxidation-liquid phase oxidation-absorption syllogic wet-dry change flue-gas denitration process, it comprises the following steps: after dedusting, enter absorption tower from boiler out flue gas, four layers of spray are comprised in absorption tower, sulfur dioxide in flue gas reacts with slurries in spraying layer, generate sulphite, and fall into bottom absorption tower with slurries, flue gas after scrubbing CO_2 enters air by the chimney at top, absorption tower, it is characterized in that: flue gas before entering absorption tower through the combined oxidation of gas phase and liquid phase.
Described a kind of gaseous oxidation-liquid phase oxidation-absorption syllogic wet-dry change flue-gas denitration process, is characterized in that: described gaseous oxidizing agent is ozone.
Described a kind of gaseous oxidation-liquid phase oxidation-absorption syllogic wet-dry change flue-gas denitration process, is characterized in that: described liquid phase oxidation agent solution is hydrogen peroxide (H
2o
2), clorox (NaClO), sodium chlorite (NaClO
2), sodium chlorate (NaClO
3), sodium peroxydisulfate (Na
2s
2o
8), potassium chlorate (KClO
3), potassium permanganate (KMnO
4), potassium bichromate (K
2cr
2o
7) in any one or a few mixing.
Described a kind of gaseous oxidation-liquid phase oxidation-absorption syllogic wet-dry change flue-gas denitration process, is characterized in that: described slurries are magnesium hydroxide solution.
Described a kind of gaseous oxidation-liquid phase oxidation-absorption syllogic wet-dry change flue-gas denitration process, it is characterized in that, this technique comprises the following steps:
(1) gaseous oxidation
Adopt ozone as gaseous oxidizing agent, make nitric oxide and ozone contact reaction in flue gas, partial oxidation becomes high-valence state nitrogen oxide;
(2) liquid phase oxidation
Oxidation of nitric oxide remaining in flue gas, as Oxygen in Liquid agent, is high-valence state nitrogen oxide by any one or a few the mixed solution in employing hydrogen peroxide, clorox, sodium chlorite, sodium chlorate, sodium peroxydisulfate, potassium chlorate, potassium permanganate, potassium bichromate;
(3) absorb
Adopt magnesium hydroxide solution as absorbent, absorb the high-valence state nitrogen oxide after Strong oxdiative in flue gas.
Described a kind of gaseous oxidation-liquid phase oxidation-absorption syllogic wet-dry change flue-gas denitration process, is characterized in that: the concentration of described gaseous oxidizing agent is 130g/m
3~ 150g/m
3.
Described a kind of gaseous oxidation-liquid phase oxidation-absorption syllogic wet-dry change flue-gas denitration process, is characterized in that: the concentration of described Oxygen in Liquid agent is 1% ~ 10%.
Implement the obvious advantage after this technology and effect is: compared with prior art, this technique first adopts the combined oxidation of gas phase and liquid phase, again by magnesium hydroxide wet absorption, achieve the target of efficient removal nitrogen oxide, reduce equipment cost and operating cost, improve denitration efficiency, be conducive to denitration technology applying in China.
Accompanying drawing explanation
Fig. 1 is gaseous oxidation-liquid phase oxidation-absorption syllogic wet-dry change flue-gas denitration process flow chart.
In figure: 1, boiler, 2, cleaner, 3, ozone purification device, 4, air-introduced machine, 5, oxidizing agent solution storage tank, 6, absorption tower, 7, absorbing liquid circulating sprayer, 8, chimney.
Detailed description of the invention
Below in conjunction with accompanying drawing, by instantiation, the invention will be further described:
As shown in Figure 1, flue gas out removes most dust flue gas through cleaner 2 from the exhaust opening of boiler 1, flue gas after removing dust enters ozone purification device 3, part oxidation of nitric oxide in flue gas is become the high-valence state nitrogen oxide that can be absorbed by slurries by ozone, ozone and flue gas mixing through air-introduced machine 4, abundant reaction, sodium chlorite solution in oxidizing agent solution storage tank 5 is sprayed to flue gas by atomizer by nitric oxide for nubbin again, be the nitrogen oxide of high-valence state by oxidation of nitric oxide remaining in flue gas, after flue gas enters absorption tower 6, four layers are divided to spray in absorption tower magnesium hydroxide solution by absorbing liquid circulating sprayer 7, by the high-valence state nox adsorption in flue gas, flue gas through absorption tower 6 can qualified discharge, flue gas directly leads to chimney 8 by the outlet at top, absorption tower.
embodiment 1: ozone oxidation NO combining hydrogen oxidation magnesium solution absorbs denitration
When flue gas enters ozone purification device, injection solubility is 150g/m
3ozone, be the nitrogen oxide of high-valence state by the oxidation of nitric oxide in flue gas, the NO after oxidation
xenter absorption tower, adopt magnesium hydroxide solution by the NO after oxidation
xabsorb, the denitration efficiency of this technique can reach 84%.
embodiment 2: sodium chlorite solution is oxidized NO combining hydrogen oxidation magnesium solution and absorbs denitration
Flue gas is after air-introduced machine, and spraying solubility by atomizer to flue gas is 3% sodium chlorite solution, is the nitrogen oxide of high-valence state by the oxidation of nitric oxide in flue gas, the NO after oxidation
xenter absorption tower, adopt magnesium hydroxide solution by the NO after oxidation
xabsorb, the denitration efficiency of this technique can reach 87%.
embodiment 3: ozone and sodium chlorite solution's combined oxidation NO combining hydrogen oxidation magnesium solution absorb denitration
When flue gas enters ozone purification device, injection solubility is 150g/m
3ozone, flue gas after air-introduced machine, by atomizer to flue gas spray solubility be 3% sodium chlorite solution, in combined oxidation flue gas, nitric oxide is converted into the nitrogen oxide of high-valence state, the NO after oxidation
xenter absorption tower, adopt magnesium hydroxide solution by the NO after oxidation
xabsorb, the denitration efficiency of this technique can reach 94%.
Claims (7)
1. gaseous oxidation-liquid phase oxidation-absorption syllogic wet-dry change flue-gas denitration process, it comprises the following steps: after dedusting, enter absorption tower from boiler out flue gas, four layers of spray are comprised in absorption tower, sulfur dioxide in flue gas reacts with slurries in spraying layer, generate sulphite, and fall into bottom absorption tower with slurries, flue gas after scrubbing CO_2 enters air by the chimney at top, absorption tower, it is characterized in that: flue gas before entering absorption tower through the secondary oxidation of gaseous oxidizing agent and Oxygen in Liquid agent.
2. a kind of gaseous oxidation-liquid phase oxidation according to claim 1-absorption syllogic wet-dry change flue-gas denitration process, is characterized in that: described gaseous oxidizing agent is ozone.
3. a kind of gaseous oxidation-liquid phase oxidation according to claim 1-absorption syllogic wet-dry change flue-gas denitration process, is characterized in that: described liquid phase oxidation agent solution is hydrogen peroxide (H
2o
2), clorox (NaClO), sodium chlorite (NaClO
2), sodium chlorate (NaClO
3), sodium peroxydisulfate (Na
2s
2o
8), potassium chlorate (KClO
3), potassium permanganate (KMnO
4), potassium bichromate (K
2cr
2o
7) in any one or a few mixing.
4. a kind of gaseous oxidation-liquid phase oxidation according to claim 1-absorption syllogic wet-dry change flue-gas denitration process, is characterized in that: described slurries are magnesium hydroxide solution.
5. a kind of gaseous oxidation-liquid phase oxidation according to claim 1-absorption syllogic wet-dry change flue-gas denitration process, it is characterized in that, this technique comprises the following steps:
(1) gaseous oxidation
Adopt ozone as gaseous oxidizing agent, make nitric oxide and ozone contact reaction in flue gas, partial oxidation becomes high-valence state nitrogen oxide;
(2) liquid phase oxidation
Oxidation of nitric oxide remaining in flue gas, as Oxygen in Liquid agent, is high-valence state nitrogen oxide by any one or a few the mixed solution in employing hydrogen peroxide, clorox, sodium chlorite, sodium chlorate, sodium peroxydisulfate, potassium chlorate, potassium permanganate, potassium bichromate;
(3) absorb
Adopt magnesium hydroxide solution as absorbent, absorb the high-valence state nitrogen oxide after Strong oxdiative in flue gas.
6. according to a kind of gaseous oxidation-liquid phase oxidation according to claim 1 or claim 2-absorption syllogic wet-dry change flue-gas denitration process, it is characterized in that: the concentration of described gaseous oxidizing agent is 130g/m
3~ 150g/m
3.
7. according to a kind of gaseous oxidation-liquid phase oxidation according to claim 1 or claim 2-absorption syllogic wet-dry change flue-gas denitration process, it is characterized in that: the concentration of described Oxygen in Liquid agent is 1% ~ 10%.
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| CN105289236A (en) * | 2015-11-23 | 2016-02-03 | 中南大学 | Synchronous desulfurization and denitrification process for reinforcing sintered flue gas based on NO oxidization by hydrogen peroxide and potassium permanganate |
| CN105457464A (en) * | 2015-11-23 | 2016-04-06 | 中南大学 | Sintering flue gas desulfurization and denitrification technology |
| CN105561751A (en) * | 2016-03-17 | 2016-05-11 | 南京格洛特环境工程股份有限公司 | Low temperature denitrification process for multi-phase catalytic oxidation and equipment thereof |
| CN105854547A (en) * | 2016-04-01 | 2016-08-17 | 河北科技大学 | Ammonia oxidizing denitration process and reaction apparatus |
| CN105964119A (en) * | 2016-05-31 | 2016-09-28 | 北京麦瑞科工业技术有限公司 | Ozone denitration device and process |
| CN106390711A (en) * | 2016-06-21 | 2017-02-15 | 秦皇岛玻璃工业研究设计院 | A denitration oxidant for glass melting furnace flue gas, a denitration device and a denitration method |
| CN106621755A (en) * | 2017-01-11 | 2017-05-10 | 长春工业大学 | Integral technology using liquid phase to jointly absorb glue gas for simultaneous desulfurizing and denitration |
| CN107243243A (en) * | 2017-05-31 | 2017-10-13 | 安徽国祯生态科技股份有限公司 | A kind of oxidation and denitration device and its method of denitration |
| CN108261900A (en) * | 2018-03-28 | 2018-07-10 | 南京工业大学 | Sectional type device and method for flue gas desulfurization and denitrification |
| CN108421396A (en) * | 2018-05-17 | 2018-08-21 | 大连铭晟环保设备有限公司 | Desulphurization denitration dust pelletizing system and desulphurization denitration dust collecting process |
| CN108452654A (en) * | 2018-03-03 | 2018-08-28 | 浙江安吉天子湖热电有限公司 | A kind of denitrification apparatus |
| CN109772136A (en) * | 2019-02-13 | 2019-05-21 | 大唐绥化热电有限公司 | Low temperature dust-removal and desulfurizing denitrification integral system and desulfurizing and denitrifying process |
| CN110052142A (en) * | 2019-04-26 | 2019-07-26 | 北京航空航天大学 | A kind of device and method for shunting ozone oxidation collaboration and absorbing flue gas desulfurization and denitrification |
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