CN103203176A - Method for flue gas desulfurization, denitrification and demercuration by semidry method - Google Patents
Method for flue gas desulfurization, denitrification and demercuration by semidry method Download PDFInfo
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- CN103203176A CN103203176A CN2013101355016A CN201310135501A CN103203176A CN 103203176 A CN103203176 A CN 103203176A CN 2013101355016 A CN2013101355016 A CN 2013101355016A CN 201310135501 A CN201310135501 A CN 201310135501A CN 103203176 A CN103203176 A CN 103203176A
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- flue gas
- composite oxidant
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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
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- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
Abstract
The invention discloses a method for flue gas desulfurization, denitrification and demercuration by a semidry method, belonging to the technical field of flue gas purification. The method comprises the following steps of: (1) spraying a composite oxidant from the bottom of a circulating fluidized bed to oxidize NO and HgO, wherein the composite oxidant is an aqueous solution containing hydrogen peroxide, an additive and a stabilizer; the additive is one or more of sodium perborate, sodium persulfate and potassium pyrosulfate; and the stabilizer is one of hydrochloric acid, sulfuric acid and perchloric acid; and (2) absorbing and removing an oxidative product and SO2 by using a calcium-based sorbent. According to the method, the composite oxidant is firstly used for oxidizing NO and HgO in flue gas, and then SO2, NO and HgO are simultaneously removed to realize integration of desulfurization, denitrification and demercuration, thus the removal rate is greatly improved, the cost is greatly reduced, and the method has high economic and environmental benefits.
Description
Technical field
The present invention relates to the flue gases purification field.
Background technology
SO in the coal-fired flue-gas
2, NO and Hg
0Life and health and ecological sustainable development to the mankind have brought serious threat.SO
2Be the main cause that produces acid rain, NO is the principal element of bringing out photochemical fog, greenhouse effects and depletion of the ozone layer, and by SO
2The aerosol that forms with NOx is to form China's major reason of haze weather on a large scale.Hg
0Have strong toxicity, volatile, difficult degradation, the aerial holdup time is long and the characteristics of long-distance migration, it has grievous injury to the human nervous system, is one of the most serious heavy metal pollution.Mercury content is higher in the used coal of China's thermoelectricity industry, and therefore, China is extremely urgent to the control of mercury in the coal-fired flue-gas.
Wet desulfurization system is to control SO at present
2Comparatively effective way, but there are shortcomings such as the big and secondary wastewater processing of floor space in it.Control to NOx then mainly utilizes SCR (SCR) denitrating system, after it is arranged in economizer.NH under the effect of catalyst
3Carry out reduction reaction with NOx, NOx is reduced to N
2And water.SCR has the high advantage of denitration efficiency, but has shortcomings such as operating cost height, ammonia leakage, catalyst poisoning and generation solid waste simultaneously.The form that exists of mercury mainly contains three kinds in the coal-fired flue-gas: simple substance attitude mercury (Hg
0), oxidation state mercury (Hg
2+) and particle mercury (Hg
p).External is active carbon injection technique (ACI) than ripe demercuration technology at present, but because active carbon is on the high side, has increased operating cost greatly, and discarded active carbon needs further the disposal.The collaborative demercuration technology of existing pollutant control appliance is present comparatively feasible way, as wet desulfurization system oxidation state mercury had removal effect preferably, electric cleaner or sack cleaner have very high capture rate to particle mercury, but above-mentioned two kinds of equipment almost do not have removal effect to simple substance mercury.
Because NO and Hg
0Dissolving hardly in the aqueous solution, and be gaseous state.Therefore, be difficult to be removed by wet desulfurization system and cleaner.And NO is about the 90-95% of NOx, Hg in the coal-fired flue-gas
0How the 30-80% that is about total mercury is with NO and Hg
0Be converted into NO
2And Hg
2+Then being absorbed in desulphurization system, is to realize the two and SO
2The key that removes simultaneously.
Summary of the invention
The invention provides a kind of method of semi-dry process flue gas desulphurization denitration demercuration, this method utilizes composite oxidant at first to the NO in the flue gas and Hg
0Carry out oxidation, realize SO then
2, NO and Hg
0Remove simultaneously, realize that desulfurization denitration demercuration is integrated, not only improved removal efficiency greatly, and greatly reduced cost, have higher economy and environmental benefit.
The technical solution used in the present invention is:
A kind of method of semi-dry process flue gas desulphurization denitration demercuration, it comprises:
(1) composite oxidant is sprayed into from the recirculating fluidized bed bottom, to NO and Hg
0Carry out oxidation; Described composite oxidant is the aqueous solution that comprises hydrogen peroxide, additive and stabilizing agent; Described additive is one or more in sodium perborate, sodium peroxydisulfate, the potassium pyrosulfate, and described stabilizing agent is a kind of in hydrochloric acid, sulfuric acid and the perchloric acid.
(2) with calcium-base absorbing agent to oxidation product and SO
2Absorb and remove.
Preferably, the concentration of primary oxidant is 3-5 mol/L in the composite oxidant, and the concentration of additive is 0.1-2 mol/L, and the concentration of stabilizing agent is 0.0001-0.005 mol/L;
The pH value of composite oxidant is 0.5-2;
Temperature in the recirculating fluidized bed is 60-120 ℃;
The flow velocity of flue gas is 1-5 L/min;
The speed of spraying into of composite oxidant is 0.5-2.0 ml/min.
This composite oxidant preparation process is: measure 3-5 mol hydrogen peroxide, 0.1-2 mol additive and 0.0001-0.005 mol stabilizing agent, additive and stabilizing agent are added in the aqueous hydrogen peroxide solution, concussion shakes up, and is diluted with water to 1L then.This composite oxidant has stronger stability, under the lucifuge condition of 24-48h, can keep higher oxidability, and the composite oxidant after the placement is to NO and Hg
0Removal efficient can reach 88% and 85%.
Technical process of the present invention is: composite oxidant sprayed into from the recirculating fluidized bed bottom, it fully mixed with flue gas, and to NO and Hg
0Carry out oxidation, the subsequent section oxidant is subjected to thermal evaporation, react with liquid and gas dual mode and gaseous contaminant, then with calcium-base absorbing agent to oxidation product and SO
2Absorb fixing.
The present invention is applicable to the polytype boiler, and can realize removing simultaneously to multiple flue gas pollutant, so this invention has good benefits in environment and economic benefit, has broad application prospects.
Hydrogen peroxide, hydroxyl radical free radical, over cure acid group, perboric acid root are the core oxides of this composite oxidant, NO, Hg in its main and flue gas
0Carry out oxidation reaction.The over cure acid group then can generate the sulfate radical free radical with hydrogen peroxide, perboric acid root and H
2Chain reaction takes place in O in course of reaction, product is hydrogen peroxide, and the generation of hydrogen peroxide can promote the generation of hydroxyl radical free radical, and the adding of stabilizing agent inorganic acid can slow down the quick decomposition of hydrogen peroxide, and promotes the generation of chain reaction.
The mechanism of action of the present invention is to utilize composite oxidant with the Hg in the flue gas
0Be oxidized to divalence mercury, NO is oxidized to NO
2, its oxidation product and SO
2Absorbed by calcium-base absorbing agent.
The concrete mechanism of action is as follows:
Adopt composite oxidant of the present invention that flue gas is carried out the desulfuration demercuration denitration and handle, treatment effect is as shown in table 1:
Table 1 desulfuration demercuration denitration effect
| Project | Before the processing | After the processing | Removal efficiency |
| Hg 0Concentration | 40
 |
3.7
 |
90.8% |
| NO concentration | 500ppm | 42ppm | 91.6% |
| SO 2Concentration | 2000ppm | 0ppm | 100% |
The time of staying of flue gas, between second, absorbing fully, the pH value of back absorption liquid was 8-10 at 3-4.
Method of the present invention can have higher removal efficiency fast with the pollutant oxidation, and desulfuration efficiency can reach 100%, and denitration and demercuration efficient can reach more than 90%.
The beneficial effect that adopts technique scheme to produce is:
1, the inventive method uniqueness utilizes composite oxidant at first to the NO in the flue gas and Hg
0Carry out oxidation, realize SO then
2, NO and Hg
0Remove simultaneously, thereby realize that desulfurization denitration demercuration is integrated, greatly reduce cost and improved removal efficiency.Thereby solved that the people that exist for a long time want to solve always and a unsolved difficult problem always.Have higher economy and environmental benefit.
2, because can be fast with the pollutant oxidation, so have higher removal efficiency.As long as operation suitably, desulfuration efficiency can reach 100%, and denitration and demercuration efficient can reach more than 90%.
The specific embodiment
Embodiment 1
The configuration composite oxidant: measure 3 mol hydrogen peroxide, 1 mol sodium perborate, 0.5 mol potassium pyrosulfate and 0.0001 mol hydrochloric acid, additive and stabilizing agent are added in the aqueous hydrogen peroxide solution, concussion shakes up, and is diluted with water to 1L then.
Above-mentioned composite oxidant is sprayed into from the recirculating fluidized bed bottom, to NO and Hg
0Carry out oxidation, then with calcium-base absorbing agent to oxidation product and SO
2Absorb fixingly, reaction condition sees Table 2.
Table 2 recirculating fluidized bed reaction condition
| Condition | Scope |
| Reaction temperature | 120℃ |
| Oxidant sample introduction speed | 0.5ml/min |
| The flue gas intake velocity | 3L/min |
| Composite oxidant pH value | 0.5-2 |
By above-mentioned condition flue gas is carried out the desulfuration demercuration denitration and handle, detection obtains: SO
2Removal efficiency be 100%, denitration efficiency is 91.7%, demercuration efficient is more than 90.8%.
Embodiment 2
The configuration composite oxidant: measure 5 mol hydrogen peroxide, 1mol sodium perborate, 0.5mol sodium peroxydisulfate, 0.5mol potassium pyrosulfate and 0.005 mol sulfuric acid, additive and stabilizing agent are added in the aqueous hydrogen peroxide solution, concussion shakes up, and is diluted with water to 1L then.
Above-mentioned composite oxidant is sprayed into from the recirculating fluidized bed bottom, to NO and Hg
0Carry out oxidation, then with calcium-base absorbing agent to oxidation product and SO
2Absorb fixingly, reaction condition sees Table 3.
Table 3 recirculating fluidized bed reaction condition
| Condition | Scope |
| Reaction temperature | 90℃ |
| Oxidant sample introduction speed | 1.0 ml/min |
| The flue gas intake velocity | 4 L/min |
| Composite oxidant pH value | 0.5-2 |
By above-mentioned condition flue gas is carried out the desulfuration demercuration denitration and handle, detection obtains: SO
2Removal efficiency be 100%, denitration efficiency is 93.0%, demercuration efficient is more than 91.2%.
Embodiment 3
The configuration composite oxidant: measure 4 mol hydrogen peroxide, 0.5mol sodium peroxydisulfate, 0.5mol potassium pyrosulfate and 0.001 mol perchloric acid, additive and stabilizing agent are added in the aqueous hydrogen peroxide solution, concussion shakes up, and is diluted with water to 1L then.
Above-mentioned composite oxidant is sprayed into from the recirculating fluidized bed bottom, to NO and Hg
0Carry out oxidation, then with calcium-base absorbing agent to oxidation product and SO
2Absorb fixingly, reaction condition sees Table 4.
Table 4 recirculating fluidized bed reaction condition
| Condition | Scope |
| Reaction temperature | 100℃ |
| Oxidant sample introduction speed | 1.5 ml/min |
| The flue gas intake velocity | 5 L/min |
| Composite oxidant pH value | 0.5-2 |
By above-mentioned condition flue gas is carried out the desulfuration demercuration denitration and handle, detection obtains: SO
2Removal efficiency be 100%, denitration efficiency is 92.3%, demercuration efficient is more than 90.6%.
Embodiment 4
The configuration composite oxidant: measure 3.5mol hydrogen peroxide, 0.5 mol potassium pyrosulfate and 0.003 mol sulfuric acid, additive and stabilizing agent are added in the aqueous hydrogen peroxide solution, concussion shakes up, and is diluted with water to 1L then.
Above-mentioned composite oxidant is sprayed into from the recirculating fluidized bed bottom, to NO and Hg
0Carry out oxidation, then with calcium-base absorbing agent to oxidation product and SO
2Absorb fixingly, reaction condition sees Table 5.
Table 5 recirculating fluidized bed reaction condition
| Condition | Scope |
| Reaction temperature | 80℃ |
| Oxidant sample introduction speed | 2.0 ml/min |
| The flue gas intake velocity | 1 L/min |
| Composite oxidant pH value | 0.5-2 |
By above-mentioned condition flue gas is carried out the desulfuration demercuration denitration and handle, detection obtains: SO
2Removal efficiency be 100%, denitration efficiency is 92.8%, demercuration efficient is more than 91.1%.
Embodiment 5
The configuration composite oxidant: measure 4.5mol hydrogen peroxide, 0.1 mol sodium peroxydisulfate and 0.004mol hydrochloric acid, additive and stabilizing agent are added in the aqueous hydrogen peroxide solution, concussion shakes up, and is diluted with water to 1L then.
Above-mentioned composite oxidant is sprayed into from the recirculating fluidized bed bottom, to NO and Hg
0Carry out oxidation, then with calcium-base absorbing agent to oxidation product and SO
2Absorb fixingly, reaction condition sees Table 6.
Table 6 recirculating fluidized bed reaction condition
| Condition | Scope |
| Reaction temperature | 60℃ |
| Oxidant sample introduction speed | 0.9 ml/min |
| The flue gas intake velocity | 2 L/min |
| Composite oxidant pH value | 0.5-2 |
By above-mentioned condition flue gas is carried out the desulfuration demercuration denitration and handle, detection obtains: SO
2Removal efficiency be 100%, denitration efficiency is 91.4%, demercuration efficient is more than 91.3%.
Claims (6)
1. the method for a semi-dry process flue gas desulphurization denitration demercuration is characterized in that comprising the steps:
(1) composite oxidant is sprayed into from the recirculating fluidized bed bottom, to NO and Hg
0Carry out oxidation; Described composite oxidant is the aqueous solution that comprises hydrogen peroxide, additive and stabilizing agent; Described additive is one or more in sodium perborate, sodium peroxydisulfate, the potassium pyrosulfate, and described stabilizing agent is a kind of in hydrochloric acid, sulfuric acid and the perchloric acid;
(2) with calcium-base absorbing agent to oxidation product and SO
2Absorb and remove.
2. the method for semi-dry process flue gas desulphurization denitration demercuration according to claim 1, the concentration that it is characterized in that hydrogen peroxide in the described composite oxidant is 3-5mol/L, the concentration of additive is 0.1-2 mol/L, and the concentration of stabilizing agent is 0.0001-0.005 mol/L.
3. the method for semi-dry process flue gas desulphurization denitration demercuration according to claim 1 is characterized in that the pH value of described composite oxidant is 0.5-2.
4. according to the method for claim 1,2 or 3 described semi-dry process flue gas desulphurization denitration demercurations, it is characterized in that the temperature in the described recirculating fluidized bed is 60-120 ℃.
5. the method for semi-dry process flue gas desulphurization denitration demercuration according to claim 4, the flow velocity that it is characterized in that described flue gas is 1-5 L/min.
6. the method for semi-dry process flue gas desulphurization denitration demercuration according to claim 5, the speed of spraying into that it is characterized in that described composite oxidant is 0.5-2.0 ml/min.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103691267A (en) * | 2013-12-19 | 2014-04-02 | 海南中航特玻材料有限公司 | Low-temperature synchronous denitration and desulfurization equipment and process for flue gas |
| CN105233687A (en) * | 2015-10-21 | 2016-01-13 | 华北电力大学（保定） | Method for removing elemental mercury in coal-fired flue gas |
| CN105903329A (en) * | 2016-06-14 | 2016-08-31 | 东莞市联洲知识产权运营管理有限公司 | Novel flue gas desulfurization and denitrification technology |
| CN106268293A (en) * | 2015-05-14 | 2017-01-04 | 王立群 | A kind of wet desulphurization denitration synergist for coal-burning boiler |
| CN109173718A (en) * | 2018-11-08 | 2019-01-11 | 华能国际电力股份有限公司 | A kind of method and device thereof of the combined desulfurization and denitration demercuration based on calcium method |
| CN109865415A (en) * | 2019-04-08 | 2019-06-11 | 福建省特种设备检验研究院 | CFB boiler, which is mixed, burns anthracite and sawdust sludge gas mercury oxidation control technique |
| CN114164004A (en) * | 2021-11-26 | 2022-03-11 | 北京市生态环境保护科学研究院 | Soil zero-valent mercury composite oxidant and method for repairing soil by using same |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103691267A (en) * | 2013-12-19 | 2014-04-02 | 海南中航特玻材料有限公司 | Low-temperature synchronous denitration and desulfurization equipment and process for flue gas |
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| CN105233687A (en) * | 2015-10-21 | 2016-01-13 | 华北电力大学（保定） | Method for removing elemental mercury in coal-fired flue gas |
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| CN109865415A (en) * | 2019-04-08 | 2019-06-11 | 福建省特种设备检验研究院 | CFB boiler, which is mixed, burns anthracite and sawdust sludge gas mercury oxidation control technique |
| CN114164004A (en) * | 2021-11-26 | 2022-03-11 | 北京市生态环境保护科学研究院 | Soil zero-valent mercury composite oxidant and method for repairing soil by using same |
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Inventor after: Zhao Yi Inventor after: Hao Runlong Inventor after: Guo Qing Inventor after: Wang Han Inventor after: Xue Fangming Inventor after: Hao Siqi Inventor before: Wang Han Inventor before: Zhao Yi Inventor before: Hao Runlong Inventor before: Hao Siqi Inventor before: Wang Li Inventor before: Guo Qing Inventor before: Du Leixia Inventor before: Cui Shuai |
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