CN102172469A - Composite flue gas purification additive for wet flue gas desulfurization system - Google Patents
Composite flue gas purification additive for wet flue gas desulfurization system Download PDFInfo
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- CN102172469A CN102172469A CN2011100560264A CN201110056026A CN102172469A CN 102172469 A CN102172469 A CN 102172469A CN 2011100560264 A CN2011100560264 A CN 2011100560264A CN 201110056026 A CN201110056026 A CN 201110056026A CN 102172469 A CN102172469 A CN 102172469A
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Abstract
The invention discloses a composite flue gas purification additive for a wet flue gas desulfurization system, which comprises the following components: (1) 360 to 1,200 mg/L hypochlorite and 0.01 to 0.1 mmol/L iron salt, magnesium salt or manganese salt; and (2) 200 to 1,000 mg/L chlorite and 0.01 to 0.1 mmol/L iron salt, magnesium slat or manganese salt. By the composite flue gas purification additive, nitrogen oxides in the main existence form of nitric oxide in flue gas can be converted into nitrogen dioxide which is easy to adsorb in the wet desulfurization device, so that the nitrogen oxides can be removed from the flue gas and the denitration efficiency can reach more than 45 percent. Meanwhile, the composite flue gas purification additive can be used for strengthening the oxide crystallization of a desulphurization byproduct and the sulfite oxidizing speed when the composite flue gas purification additive is applied can reach 2.5 to 8 times of the sulfite oxidizing speed when the composite flue gas purification additive is not applied, so that the problem that a desulphurization product is insufficiently oxidized is effectively solved and the availability ratio of a system is ensured. The composite flue gas purification additive is convenient to operate and has good economic and environment benefits.
Description
Technical field
The present invention relates to combustion apparatus, relate in particular to a kind of compound gas cleaning additive that is used for the combustion apparatus wet desulfurization system.
Background technology
China's rapid development of economy has caused the great demand to the energy, and 1978-2009, disposable energy-consuming was brought up to 30.2 hundred million tons from 5.7 hundred million tons (standard coals).The ratio of coal in China in the primary energy production and consumption accounts for more than 70% for a long time, and consume about 75% be used for burning, produced a large amount of SO
2Deng pollutant.According to statistics, China SO
2Discharge capacity 90% from fire coal, by SO
2The acid rain area that pollution causes accounts for 30% of the total area in the whole nation, has caused the serious environmental pollution, has caused enormous economic loss, has a strong impact on the healthy of people simultaneously, has become one of key factor of restriction social sustainable development.According to the measuring and calculating of former State Environmental Protection Administration report, discharge 1 ton of SO
2The economic loss that causes is about 20,000 yuans, and according to the total emission volumn of 2009 2214.4 ten thousand t, whole nation loss is 4428.8 hundred million yuan, accounts for 1.32% of GDP then.Wherein, the thermoelectricity industry is China SO
2The key industry of control, thermoelectricity industry discharging SO in 2009
2Reach 9,480,000 tons, account for China SO then
243% of total emission volumn, the people who is China's maximum is SO
2Emission source.Along with China's sustained and rapid development of economy, electricity needs is continued to increase, the leading position of coal electricity can not change in the quite a long period from now on, is still China SO
2The key point of control.
Flue gas desulfurization is China current combustion equipment SO
2The main means of control.The Eleventh Five-Year Plan period, under the promotion of state compulsion policy, China's desulfurization industry has obtained rapid growth, by the end of the year 2009, power plants flue gas desulfurization installation is above 4.70 hundred million kilowatts, account for 71% of whole fired power generating unit capacity, wherein adopted wet process of FGD technology such as limestone-gypsum method, seawater method and magnesium method more than 94%, this technology realizes SO by alkaline absorption solution with contacting of flue gas
2Remove, but since in the flue gas NOx mainly exist with the form of NO, and NO is owing to be difficult to water-solublely so can't be removed, in addition, desulfurization method of limestone-gypsum is usually because product dysoxidations such as calcium sulfite etc. influence the quality of desulfurization product-gypsum.At present, China's " thermal power plant's atmosphere pollutants emission standards " revises, and new standard is further being strengthened SO
2In control time, also proposed more strict limit value to NOx, therefore, how to utilize the present desulfurization facility that has built up to realize simultaneously effective control to NOx having become the present pressing issues that face of China.
Therefore, exploitation can be used for the compound gas cleaning additive of wet method fume desulfurizing system, by in the absorption liquid of existing desulphurization system, adding a small amount of compound gas cleaning additive to realize effectively removing of NOx, avoid adding again relevant denitration facility, the oxidation and the crystallization process that improve the wet process of FGD product simultaneously improve the removal effect of wet flue gas desulfurization tower to sulfur dioxide in flue gas, to reducing combustion equipment desulphurization denitration cost, promoting the development of China's flue gas desulfurization and denitrification industry to have great importance.
Current combustion is equipped especially, and wet fuel gas desulfurizing technologies such as thermal power plant's limestone-gypsum method, seawater method and magnesium method have the following disadvantages: the one, and desulfurizer can't remove the NOx in the flue gas effectively in desulfurization, need build corresponding denitration facility in addition, complex process, the denitration cost is higher; The 2nd, the wet fuel gas desulfurizing technologies such as limestone-gypsum method that extensively adopt usually because product dysoxidations such as calcium sulfite etc. influence the quality of desulfurization product-gypsum, have reduced system's availability at present, have influenced the desulfurized effect of wet method fume desulfurizing system.
Summary of the invention
The objective of the invention is to overcome the especially above deficiency of wet fuel gas desulfurizing technologies existence such as thermal power plant's limestone-gypsum method, seawater method and magnesium method of existing combustion equipment, a kind of compound gas cleaning additive that is used for the combustion apparatus wet desulfurization system is provided.
The component that compound gas cleaning additive is used for wet method fume desulfurizing system is: (1) hypochlorite concentration is 360～1200mg/L, and molysite, magnesium salts or manganese salinity are 0.01～0.1mmol/L; (2) chlorite concentration is 200～1000mg/L, and molysite, magnesium salts or manganese salinity are 0.01～0.1mmol/L.
The component that compound gas cleaning additive is used for wet method fume desulfurizing system is: (1) hypochlorite concentration is 550～1050mg/L, and molysite, magnesium salts or manganese salinity are 0.03～0.1mmol/L; (2) chlorite concentration is 450～900mg/L, and molysite, magnesium salts or manganese salinity are 0.03～0.1mmol/L.
Described hypochlorite is calcium hypochlorite or clorox, and chlorite is a sodium chlorite, and molysite is a ferric sulfate, and magnesium salts is a magnesium sulfate, and manganese salt is manganese sulfate.
The present invention can be in wet desulphurization device will be the nitrogen dioxide that the conversion of nitrogen oxides of main existence form becomes to be easy to absorb with nitric oxide in the flue gas, thereby realizes effectively removing of nitrogen oxide in the flue gas, and maximum denitration efficiency can reach more than 45%; Simultaneously, the present invention can strengthen the oxidizing and crystallizing process of accessory substance, and the inferior sulfate radical oxidation rate can reach the 2.5-8 that do not use when of the present invention doubly, thereby effectively overcomes the dysoxidative difficult problem of desulfurization product, guarantees system's availability.
The present invention can be used for the wet method fume desulfurizing systems such as limestone-gypsum method, magnesium method and seawater method that various combustion apparatus is equipped with, can reach the purpose of utilizing wet method fume desulfurizing system to remove nitrogen oxide simultaneously, easy to operate, have good economic benefits and environmental benefit.
Description of drawings
Fig. 1 adds the influence of compound gas cleaning additive to desulphurization system outlet NOx concentration;
Fig. 2 is the influence of compound gas cleaning additive to the desulphurization system oxidizing reaction rate.
The specific embodiment
The compound gas cleaning additive that is used for the combustion apparatus wet desulfurization system is mainly by hypochlorite that can promote oxidation of nitric oxide or chlorite, and molysite, magnesium salts or the manganese salt composition that can improve desulfurization product oxidation and crystallization.Wherein,
The component that compound gas cleaning additive is used for wet method fume desulfurizing system is: (1) hypochlorite concentration is 360～1200mg/L, and molysite, magnesium salts or manganese salinity are 0.01～0.1mmol/L; (2) chlorite concentration is 200～1000mg/L, and molysite, magnesium salts or manganese salinity are 0.01～0.1mmol/L.
The component that compound gas cleaning additive is used for wet method fume desulfurizing system is: (1) hypochlorite concentration is preferably 550～1050mg/L, and molysite, magnesium salts or manganese salinity are preferably 0.03～0.1mmol/L; (2) chlorite concentration is preferably 450～900mg/L, and molysite, magnesium salts or manganese salinity are preferably 0.03～0.1mmol/L.
Described hypochlorite is calcium hypochlorite or clorox, and chlorite is a sodium chlorite, and molysite is a ferric sulfate, and magnesium salts is a magnesium sulfate, and manganese salt is manganese sulfate.
The flue gas that combustion apparatus produces connects flue via the wet flue gas desulfurization tower inlet and enters wet flue gas desulfurization tower, by in the absorption liquid of wet flue gas desulfurization tower, adding compound gas cleaning additive, to be that the conversion of nitrogen oxides of main existence form becomes the nitrogen dioxide be easy to absorb with nitric oxide in the flue gas, thereby realize effectively removing of nitrogen oxide in the flue gas; Compound gas cleaning additive can also improve the availability of desulphurization system by oxidation and the crystallization process that improves the wet process of FGD product, improves the desulfurized effect of wet process of FGD facility.
Principle of the present invention is:
1) NO's removes reaction
NO+ClO
-→Cl
-+NO
2
NO
2+H
2O→NO
3 -
2) M
N+The oxidation of inferior sulfate radical
SO
3 2-+O
2→SO
4 2-
In the formula, M
N+Be Fe
3+, Mg
2+Or Mn
2+Deng metal cation.
Flue gas after being purified connects flue via the anti-tower outlet of wet process of FGD and imports chimney, discharges via chimney.
Fig. 1 is the application result of the compound gas cleaning additive of the present invention on certain 300MW coal fired power generation unit limestone-gypsum wet flue gas desulfurizer.The engineering application result shows that the present invention can remove the NOx in the flue gas effectively, add this compound gas cleaning additive after, the denitration efficiency of limestone-gypsum wet process of FGD facility reaches 45%, is promptly realizing SO
2Can realize removing of NOx effectively when reducing discharging.
Fig. 2 is the influence situation of the compound gas cleaning additive of the present invention to oxidizing reaction rate, and result of study shows: in the 0.01mmol-0.1mmol/L concentration range, magnesium ion can improve inferior sulfate radical oxidation rate 2.5-4.5 doubly; Iron ion can improve inferior sulfate radical oxidation rate 4-5.5 doubly; Manganese ion can improve inferior sulfate radical oxidation rate 6-8 doubly.Compound gas cleaning additive can significantly improve system's oxidation rate, strengthens the oxidizing and crystallizing process of accessory substance, overcomes the dysoxidative difficult problem of desulfurization product, guarantees system's availability.
Claims (3)
1. compound gas cleaning additive that is used for wet method fume desulfurizing system, it is characterized in that the component that compound gas cleaning additive is used for wet method fume desulfurizing system is: (1) hypochlorite concentration is 360～1200mg/L, and molysite, magnesium salts or manganese salinity are 0.01～0.1mmol/L; (2) chlorite concentration is 200～1000mg/L, and molysite, magnesium salts or manganese salinity are 0.01～0.1mmol/L.
2. a kind of compound gas cleaning additive that is used for wet method fume desulfurizing system according to claim 1, it is characterized in that the component that compound gas cleaning additive is used for wet method fume desulfurizing system is: (1) hypochlorite concentration is 550～1050mg/L, and molysite, magnesium salts or manganese salinity are 0.03～0.1mmol/L; (2) chlorite concentration is 450～900mg/L, and molysite, magnesium salts or manganese salinity are 0.03～0.1mmol/L.
3. a kind of compound gas cleaning additive that is used for wet method fume desulfurizing system according to claim 1 and 2, it is characterized in that described hypochlorite is calcium hypochlorite or clorox, chlorite is a sodium chlorite, and molysite is a ferric sulfate, magnesium salts is a magnesium sulfate, and manganese salt is manganese sulfate.
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| CN105854574A (en) * | 2016-04-26 | 2016-08-17 | 无锡锡能锅炉有限公司 | Pulverized coal boiler flue gas desulfurization process |
| CN106606922A (en) * | 2016-12-26 | 2017-05-03 | 合肥天翔环境工程有限公司 | Method for simultaneous desulfurization and denitrification of flue gas through wet method |
| CN109173638A (en) * | 2018-10-30 | 2019-01-11 | 攀钢集团攀枝花钢铁研究院有限公司 | Low temperature NO oxidant and preparation method thereof |
| CN109621669A (en) * | 2018-12-14 | 2019-04-16 | 四川龙蟒钛业股份有限公司 | A kind of method of promotor auxiliary sulfuric acid titanium white calcining tail gas desulfurization denitration |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105854574A (en) * | 2016-04-26 | 2016-08-17 | 无锡锡能锅炉有限公司 | Pulverized coal boiler flue gas desulfurization process |
| CN106606922A (en) * | 2016-12-26 | 2017-05-03 | 合肥天翔环境工程有限公司 | Method for simultaneous desulfurization and denitrification of flue gas through wet method |
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| CN109621669A (en) * | 2018-12-14 | 2019-04-16 | 四川龙蟒钛业股份有限公司 | A kind of method of promotor auxiliary sulfuric acid titanium white calcining tail gas desulfurization denitration |
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Application publication date: 20110907 |