CN103203176B - 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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- CN103203176B CN103203176B CN201310135501.6A CN201310135501A CN103203176B CN 103203176 B CN103203176 B CN 103203176B CN 201310135501 A CN201310135501 A CN 201310135501A CN 103203176 B CN103203176 B CN 103203176B
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- flue gas
- composite oxidant
- demercuration
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- oxidant
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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 flue gases purification field.
Background technology
SO in coal-fired flue-gas
2, NO and Hg
0serious threat is brought to the life and health of the mankind and the sustainable development of ecology.SO
2be produce the main cause of acid rain, NO is the principal element of bringing out photochemical fog, greenhouse effects and depletion of the ozone layer, and by SO
2with the major reason that the aerosol of NOx formation is the Chinese wide range of haze weather of formation.Hg
0have the feature of strong toxicity, volatile, difficult degradation, aerial holdup time long and long-distance migration, it has grievous injury to human nervous system, is one of the most serious heavy metal pollution.China's Thermal Power Generation Industry Mercury in Coal used content is higher, and therefore, the control of China to Mercury In Coal Combustion Flue Gas is extremely urgent.
Wet desulfurization system is control SO at present
2comparatively effective way, but there is the shortcomings such as the large and secondary wastewater process of floor space in it.SCR (SCR) denitrating system is then mainly utilized, after it is arranged in economizer to the control of NOx.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 that operating cost is high, the shortcoming such as NH_3 leakage, catalyst poisoning and generation solid waste simultaneously.The existing forms of Mercury In Coal Combustion Flue Gas mainly contains three kinds: elemental mercury (Hg
0), oxidation state mercury (Hg
2+) and particle mercury (Hg
p).External more ripe demercuration technology is at present active carbon injection technique (ACI), but due to active carbon on the high side, considerably increase operating cost, and discarded active carbon needs to dispose further.Existing pollutant catabolic gene equipment collaboration demercuration technology is way comparatively feasible at present, as wet desulfurization system has good removal effect to oxidation state mercury, 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 Elemental Mercury.
Due to NO and Hg
0dissolve hardly in aqueous, 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 in coal-fired flue-gas, Hg
0be about the 30-80% of total mercury, how by NO and Hg
0be converted into NO
2and Hg
2+then being absorbed in desulphurization system, is both realizations and SO
2the key simultaneously removed.
Summary of the invention
The invention provides a kind of method of semi-dry process flue gas desulphurization denitration demercuration, the method utilizes composite oxidant first to NO and Hg in flue gas
0be oxidized, then realize SO
2, NO and Hg
0remove simultaneously, realize desulfurization denitration demercuration integration, not only substantially increase removal efficiency, and greatly reduce cost, there is higher economy and environment benefit.
The technical solution used in the present invention is:
A method for semi-dry process flue gas desulphurization denitration demercuration, it comprises:
(1) composite oxidant is sprayed into, to NO and Hg bottom recirculating fluidized bed
0be oxidized; Described composite oxidant is the aqueous solution comprising hydrogen peroxide, additive and stabilizing agent; Described additive is one or more in sodium perborate, sodium peroxydisulfate, potassium pyrosulfate, and described stabilizing agent is the one in hydrochloric acid, sulfuric acid and perchloric acid.
(2) with calcium-base absorbing agent to oxidation product and SO
2carry out absorbing and removing.
Preferably, in composite oxidant, the concentration of primary oxidant is 3-5 mol/L, 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 recirculating fluidized bed is 60-120 DEG C;
The flow velocity of flue gas is 1-5 L/min;
The speed that sprays 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, add in aqueous hydrogen peroxide solution by additive and stabilizing agent, concussion shakes up, and is then diluted with water to 1L.This composite oxidant has stronger stability, and under the lucifuge condition of 24-48h, can maintain higher oxidability, the composite oxidant after placement is to NO and Hg
0removal efficiency can reach 88% and 85%.
Technical process of the present invention is: sprayed into bottom recirculating fluidized bed by composite oxidant, makes it fully mix with flue gas, and to NO and Hg
0be oxidized, subsequent section oxidant by thermal evaporation, reacts with liquid and gas two kinds of modes and gaseous contaminant, then with calcium-base absorbing agent to oxidation product and SO
2carry out absorption to fix.
The present invention is applicable to polytype boiler, and can realize removing to multiple flue gas pollutant simultaneously, and therefore this invention has good environmental benefit 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.Over cure acid group then can generate potentiometric titrations with hydrogen peroxide, perboric acid root and H
2there is chain reaction in O, product is hydrogen peroxide, and the generation of hydrogen peroxide can promote the generation of hydroxyl radical free radical in course of reaction, and stabilizing agent inorganic acid add the fast decoupled that can slow down hydrogen peroxide, and promote the generation of chain reaction.
The mechanism of action of the present invention utilizes composite oxidant by the Hg in flue gas
0be oxidized to bivalent 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 to carry out desulfuration demercuration denitration process to flue gas, treatment effect is as shown in table 1:
Table 1 desulfuration demercuration denitration effect
| Project | Before process | After process | Removal efficiency |
| Hg 0Concentration | 40 | 3.7 | 90.8% |
| NO concentration | 500ppm | 42ppm | 91.6% |
| SO 2Concentration | 2000ppm | 0ppm | 100% |
Time of staying of flue gas, absorbing the pH value of absorbing liquid was completely 8-10 between 3-4 second.
Pollutant can be oxidized by method of the present invention fast, and have higher removal efficiency, desulfuration efficiency can reach 100%, and denitration and demercuration efficiency can reach more than 90%.
The beneficial effect adopting technique scheme to produce is:
1, the inventive method is unique, utilizes composite oxidant first to NO and Hg in flue gas
0be oxidized, then realize SO
2, NO and Hg
0remove simultaneously, thus realize desulfurization denitration demercuration integration, greatly reduce cost and improve removal efficiency.Thus solve the people existed for a long time and want to solve and a unsolved difficult problem always always.There is higher economy and environment benefit.
2, owing to being oxidized by pollutant fast, therefore there is higher removal efficiency.As long as suitably, desulfuration efficiency can reach 100%, and denitration and demercuration efficiency can reach more than 90% in operation.
Detailed description of the invention
Embodiment 1
Configuration composite oxidant: measure 3 mol hydrogen peroxide, 1 mol sodium perborate, 0.5 mol potassium pyrosulfate and 0.0001 mol hydrochloric acid, add in aqueous hydrogen peroxide solution by additive and stabilizing agent, concussion shakes up, and is then diluted with water to 1L.
Above-mentioned composite oxidant is sprayed into, to NO and Hg bottom recirculating fluidized bed
0be oxidized, then with calcium-base absorbing agent to oxidation product and SO
2carry out absorption to fix, reaction condition is in table 2.
Table 2 recirculating fluidized bed reaction condition
| Condition | Scope |
| Reaction temperature | 120℃ |
| Oxidant sample introduction speed | 0.5ml/min |
| Flue gas intake velocity | 3L/min |
| Composite oxidant pH value | 0.5-2 |
Carry out desulfuration demercuration denitration process by above-mentioned condition to flue gas, detection obtains: SO
2removal efficiency be 100%, denitration efficiency is 91.7%, and demercuration efficiency is more than 90.8%.
Embodiment 2
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, add in aqueous hydrogen peroxide solution by additive and stabilizing agent, concussion shakes up, and is then diluted with water to 1L.
Above-mentioned composite oxidant is sprayed into, to NO and Hg bottom recirculating fluidized bed
0be oxidized, then with calcium-base absorbing agent to oxidation product and SO
2carry out absorption to fix, reaction condition is in table 3.
Table 3 recirculating fluidized bed reaction condition
| Condition | Scope |
| Reaction temperature | 90℃ |
| Oxidant sample introduction speed | 1.0 ml/min |
| Flue gas intake velocity | 4 L/min |
| Composite oxidant pH value | 0.5-2 |
Carry out desulfuration demercuration denitration process by above-mentioned condition to flue gas, detection obtains: SO
2removal efficiency be 100%, denitration efficiency is 93.0%, and demercuration efficiency is more than 91.2%.
Embodiment 3
Configuration composite oxidant: measure 4 mol hydrogen peroxide, 0.5mol sodium peroxydisulfate, 0.5mol potassium pyrosulfate and 0.001 mol perchloric acid, add in aqueous hydrogen peroxide solution by additive and stabilizing agent, concussion shakes up, and is then diluted with water to 1L.
Above-mentioned composite oxidant is sprayed into, to NO and Hg bottom recirculating fluidized bed
0be oxidized, then with calcium-base absorbing agent to oxidation product and SO
2carry out absorption to fix, reaction condition is in table 4.
Table 4 recirculating fluidized bed reaction condition
| Condition | Scope |
| Reaction temperature | 100℃ |
| Oxidant sample introduction speed | 1.5 ml/min |
| Flue gas intake velocity | 5 L/min |
| Composite oxidant pH value | 0.5-2 |
Carry out desulfuration demercuration denitration process by above-mentioned condition to flue gas, detection obtains: SO
2removal efficiency be 100%, denitration efficiency is 92.3%, and demercuration efficiency is more than 90.6%.
Embodiment 4
Configuration composite oxidant: measure 3.5mol hydrogen peroxide, 0.5 mol potassium pyrosulfate and 0.003 mol sulfuric acid, add in aqueous hydrogen peroxide solution by additive and stabilizing agent, concussion shakes up, and is then diluted with water to 1L.
Above-mentioned composite oxidant is sprayed into, to NO and Hg bottom recirculating fluidized bed
0be oxidized, then with calcium-base absorbing agent to oxidation product and SO
2carry out absorption to fix, reaction condition is in table 5.
Table 5 recirculating fluidized bed reaction condition
| Condition | Scope |
| Reaction temperature | 80℃ |
| Oxidant sample introduction speed | 2.0 ml/min |
| Flue gas intake velocity | 1 L/min |
| Composite oxidant pH value | 0.5-2 |
Carry out desulfuration demercuration denitration process by above-mentioned condition to flue gas, detection obtains: SO
2removal efficiency be 100%, denitration efficiency is 92.8%, and demercuration efficiency is more than 91.1%.
Embodiment 5
Configuration composite oxidant: measure 4.5mol hydrogen peroxide, 0.1 mol sodium peroxydisulfate and 0.004mol hydrochloric acid, add in aqueous hydrogen peroxide solution by additive and stabilizing agent, concussion shakes up, and is then diluted with water to 1L.
Above-mentioned composite oxidant is sprayed into, to NO and Hg bottom recirculating fluidized bed
0be oxidized, then with calcium-base absorbing agent to oxidation product and SO
2carry out absorption to fix, reaction condition is in table 6.
Table 6 recirculating fluidized bed reaction condition
| Condition | Scope |
| Reaction temperature | 60℃ |
| Oxidant sample introduction speed | 0.9 ml/min |
| Flue gas intake velocity | 2 L/min |
| Composite oxidant pH value | 0.5-2 |
Carry out desulfuration demercuration denitration process by above-mentioned condition to flue gas, detection obtains: SO
2removal efficiency be 100%, denitration efficiency is 91.4%, and demercuration efficiency is more than 91.3%.
Claims (3)
1. a method for semi-dry process flue gas desulphurization denitration demercuration, is characterized in that comprising the steps:
(1) composite oxidant is sprayed into bottom recirculating fluidized bed, make it fully mix with flue gas, to NO and Hg
0be oxidized, subsequent section composite oxidant, by thermal evaporation, reacts with liquid and gas two kinds of modes and gaseous contaminant; Described composite oxidant is the aqueous solution comprising hydrogen peroxide, additive and stabilizing agent; Described additive is one or more in sodium perborate, sodium peroxydisulfate, potassium pyrosulfate, and described stabilizing agent is the one in hydrochloric acid, sulfuric acid and perchloric acid;
(2) with calcium-base absorbing agent to oxidation product and SO
2carry out absorbing and removing;
In described composite oxidant, the concentration of hydrogen peroxide is 3-5mol/L, 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 described composite oxidant is 0.5-2; Temperature in described recirculating fluidized bed is 60-120 DEG C.
2. the method for semi-dry process flue gas desulphurization denitration demercuration according to claim 1, is characterized in that the flow velocity of described flue gas is 1-5 L/min.
3. the method for semi-dry process flue gas desulphurization denitration demercuration according to claim 2, is characterized in that the speed that sprays into of described composite oxidant is 0.5-2.0 ml/min.
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| CN103691267B (en) * | 2013-12-19 | 2016-09-07 | 海南中航特玻材料有限公司 | A kind of flue gas low-temperature synchronizes denitration desulphurization plant and technique |
| CN106268293A (en) * | 2015-05-14 | 2017-01-04 | 王立群 | A kind of wet desulphurization denitration synergist for coal-burning boiler |
| CN105233687B (en) * | 2015-10-21 | 2018-01-02 | 华北电力大学（保定） | A kind of method of elemental mercury in removing coal-fired flue-gas |
| CN105903329B (en) * | 2016-06-14 | 2018-06-29 | 广东万引科技发展有限公司 | A kind of flue gas desulfurization and denitration technique |
| 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 |
| CN114164004B (en) * | 2021-11-26 | 2023-06-13 | 北京市生态环境保护科学研究院 | Soil zero-valent mercury composite oxidant and method for restoring soil by using same |
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| US5980847A (en) * | 1995-04-24 | 1999-11-09 | Mitsubishi Materials Corporation | Method for removing nitrogen oxide |
| JP3711490B2 (en) * | 2001-06-01 | 2005-11-02 | 独立行政法人科学技術振興機構 | Method and apparatus for oxidizing SO2 in exhaust gas using HO2 radical as OH generating reactive species in radical chain reaction of SO2 oxidation |
| US7404938B2 (en) * | 2004-05-11 | 2008-07-29 | The United States Of America As Represented By The Administrator Of The National Aeronautics And Space Administration | Emission control system |
| CN1962034A (en) * | 2006-10-25 | 2007-05-16 | 华北电力大学 | Method and apparatus for removing sulfur, nitrate and mercury simultaneously from boiler flue gas |
| CN101337153B (en) * | 2008-08-12 | 2011-08-31 | 东南大学 | Ultrasonic integrated desulfurization denitration demercuration method and device thereof |
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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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