CN113677421B - Method and device for simultaneously removing sulfur oxides and nitrogen oxides contained in exhaust gas - Google Patents
Method and device for simultaneously removing sulfur oxides and nitrogen oxides contained in exhaust gas Download PDFInfo
- Publication number
- CN113677421B CN113677421B CN202080027806.3A CN202080027806A CN113677421B CN 113677421 B CN113677421 B CN 113677421B CN 202080027806 A CN202080027806 A CN 202080027806A CN 113677421 B CN113677421 B CN 113677421B
- Authority
- CN
- China
- Prior art keywords
- exhaust gas
- reaction
- absorbent
- organic acid
- desulfurization
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/75—Multi-step processes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/46—Removing components of defined structure
- B01D53/60—Simultaneously removing sulfur oxides and nitrogen oxides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/14—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by absorption
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/14—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by absorption
- B01D53/1493—Selection of liquid materials for use as absorbents
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/46—Removing components of defined structure
- B01D53/54—Nitrogen compounds
- B01D53/56—Nitrogen oxides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/76—Gas phase processes, e.g. by using aerosols
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/77—Liquid phase processes
- B01D53/78—Liquid phase processes with gas-liquid contact
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/77—Liquid phase processes
- B01D53/79—Injecting reactants
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2251/00—Reactants
- B01D2251/10—Oxidants
- B01D2251/104—Ozone
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2251/00—Reactants
- B01D2251/40—Alkaline earth metal or magnesium compounds
- B01D2251/404—Alkaline earth metal or magnesium compounds of calcium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2251/00—Reactants
- B01D2251/60—Inorganic bases or salts
- B01D2251/604—Hydroxides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2251/00—Reactants
- B01D2251/60—Inorganic bases or salts
- B01D2251/606—Carbonates
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2251/00—Reactants
- B01D2251/70—Organic acids
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2258/00—Sources of waste gases
- B01D2258/02—Other waste gases
- B01D2258/0283—Flue gases
-
- 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
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Biomedical Technology (AREA)
- Dispersion Chemistry (AREA)
- Treating Waste Gases (AREA)
Abstract
The present application relates to a method and apparatus for simultaneously removing sulfur oxides and nitrogen oxides contained in exhaust gas, and more particularly, to a method and apparatus for simultaneously removing sulfur oxides and nitrogen oxides contained in exhaust gas, which can simultaneously perform a denitrification process and a desulfurization process of exhaust gas in one wet process equipment by performing a denitrification process of exhaust gas through a wet process under the same operation conditions as those of the desulfurization process.
Description
Technical Field
The present application relates to a method and apparatus for simultaneously removing sulfur oxides and nitrogen oxides contained in exhaust gas, and more particularly, to a method and apparatus for simultaneously removing sulfur oxides and nitrogen oxides contained in exhaust gas by a wet method.
Background
When fossil fuel is burned, sulfur in the fuel is oxidized to thereby generate sulfur dioxide as sulfur oxide, and nitrogen components in the fuel are oxidized or combustion air is decomposed at high temperature to inevitably generate nitrogen oxides (NO x ). When sulfur oxide (SO x ) And Nitrogen Oxides (NO) x ) When discharged to the atmosphere, the particles combine with water vapor, inorganic substances, and the like in the air to form fine particles having PM of 2.5 or less, and become a main atmospheric pollutant for reducing the visible distance and inducing cardiopulmonary diseases (korean society of atmospheric environment, volume 3, phase 2, month 2015, month 4, pages 143 to 156).
Removal of Sulfur Oxides (SO) in atmospheric pollution discharge equipment using fossil fuels x ) A limestone wet desulfurization apparatus is generally used, but the desulfurization rate is 80% to 90%, and therefore, a part of the amount of produced gas is discharged to the atmosphere.
In addition, for removing nitrogen oxides (NO X ) The most common and effective denitrification method is the Selective Catalytic Reduction (SCR) method, but the denitrification rate is only 70% to 90%, so that 10% to 30% of the production amount is inevitably discharged into the atmosphere. Therefore, in order to improve the quality of the atmospheric environment, development of a technique for further reducing the emission is required.
Generally, an atmospheric pollution control apparatus using fossil fuel is arranged in the order of a selective catalytic reduction method, an electric dust collector, and flue gas desulfurization (Flue gas desulfurization, FGD). The selective catalytic reduction method is to reduce nitrogen oxides to nitrogen (N) by injecting ammonia or urea in a gaseous state 2 ) Is used for removing nitrogen oxides. In the flue gas desulfurization apparatus, a limestone slurry is sprayed to remove sulfur dioxide (SO 2 ) The gas is absorbed and oxidized by the limestone slurry, and sulfur dioxide is removed in a manner of being converted into solid gypsum. However, if the injection amount of the denitrification agent and the desulfurization agent is increased to improve the removal rate, the increased unreacted materials may cause malfunction of the apparatus.
Residual Nitrogen Oxides (NO) which are not removed even when treated by the selective catalytic reduction method x ) Most of them are insoluble Nitric Oxide (NO), and therefore are not removed in the absorber of the flue gas desulfurization apparatus and are inevitably discharged to the atmosphere. For more complete removal, development of wet denitrification technology for removing nitrogen oxides by an absorption method in an absorption tower of a flue gas desulfurization apparatus is required.
As a related art, a method for preparing nitrogen oxides by plasma and mixing them with Na is disclosed 2 S、Na 2 SO 3 Method for removing nitrogen oxides by reaction (Korean patent No. 10-1800517 (bulletin day: 2017.11.23), moo beer Chang, how Ming Lee, feeling Wu&Chi Ren Lai, journal of the society of air and waste management, 54:941-949), additionally discloses the conversion of SO x 、NO x Adsorption in alcohols or glycols as organic solvents to remove SO x 、NO x The method of korean patent No. 10-1871197 (bulletin day: 2018.06.27)), these prior arts have the following problems: in order to simultaneously treat desulfurization and denitrification, further use of expensive Na is required 2 S、Na 2 SO 3 And it is required to additionally prepare a desulfurization and denitrification solution for use as a complex solution comprising polyol and/or polyethylene glycol, and it is required to adjust the temperature of flue gas before desulfurization and denitrification is performed, and there are problems such as treatment of desulfurization wastewater. There is a limit in practical use.
In addition, korean patent laid-open No. 10-1724358 (bulletin day: 2017.04.10) discloses the following: a method of oxidizing a flue gas with ozone and then adsorbing the oxidized flue gas in an adsorption tower by droplets produced from hydrogen peroxide. Korean laid-open patent No. 10-2017-0021713 (publication date: 2017.02.28) discloses an electrolysis apparatus for trapping nitrides of exhaust gas by causing redox reaction of Fe-EDTA by supplying electric energy. These prior art techniques have problems such as the need to build new processes.
Accordingly, there is a need to develop a more efficient desulfurization and denitrification process technology SO that the safety and environmental problems associated with the existing desulfurization process can be solved, while SO can be increased without adding equipment x NO and NO x Is not limited, and the simultaneous removal rate of the same is not limited.
Disclosure of Invention
Problems to be solved by the application
The main object of the present application is to provide a method and apparatus for simultaneously removing sulfur oxides and nitrogen oxides contained in exhaust gas, which can simultaneously perform a denitrification process and a desulfurization process of exhaust gas by one wet treatment process, and can economically treat both sulfur oxides and nitrogen oxides without changing equipment for denitrification or adding expensive denitrification additives in the existing wet desulfurization process operated.
Solution for solving the problem
In order to achieve the above object, an integrated embodiment of the present application provides a method for simultaneously removing sulfur oxides and nitrogen oxides contained in exhaust gas, comprising: (a) A step of oxidizing nitrogen oxides contained in the exhaust gas by reacting the exhaust gas with ozone; (b) A step of obtaining an absorbent by mixing an organic acid or an organic acid salt in an alkaline earth metal compound in an aqueous solution state or a slurry state; and (c) a step of bringing the exhaust gas oxidized by the reaction with ozone in the step (a) into contact with the absorbent in the step (b) to thereby denitrify and desulfurize the exhaust gas.
In a preferred embodiment of the present application, the alkaline earth metal compound of step (b) is selected from the group consisting of calcium carbonate, calcium hydroxide and mixtures thereof.
In a preferred embodiment of the present application, the organic acid in the step (b) is selected from the group consisting of RCOOH (r=h or alkyl group having 1 to 18 carbon atoms), dicarboxylic acid having 1 to 20 carbon atoms, and a mixture thereof.
In a preferred embodiment of the present application, the organic acid or organic acid salt in the step (b) is contained in an amount of 1ppm to 3000ppm based on the solid content in the absorbent.
In a preferred embodiment of the present application, the step (a) includes: oxidizing Nitric Oxide (NO) contained in the exhaust gas into nitrogen dioxide (NO) by reacting the exhaust gas with ozone 2 ) Is carried out by a method comprising the steps of.
In a preferred embodiment of the present application, the desulfurization in the step (c) is a desulfurization reaction performed by a reaction between an alkaline earth metal compound in the absorbent and an oxide of sulfur in the exhaust gas. The denitrification in the step (c) is nitrogen dioxide (NO) obtained by reacting an alkaline earth metal sulfite formed by a desulfurization reaction of a sulfur oxide of the exhaust gas and an alkaline earth metal compound in the absorbent with Nitric Oxide (NO) contained in the exhaust gas and ozone 2 ) Is carried out by the reaction of the catalyst.
In other embodiments of the present application, there is provided an apparatus for simultaneously removing sulfur oxides and nitrogen oxides contained in exhaust gas, comprising: a gas phase reaction unit that oxidizes nitrogen oxides contained in the exhaust gas by reacting the exhaust gas with ozone; an absorbent storage unit for storing an absorbent by mixing an organic acid or an organic acid salt with an alkaline earth metal compound in an aqueous solution state or a slurry state; and a wet reaction unit configured to perform denitrification and desulfurization of the exhaust gas containing sulfur oxides and nitrogen oxides by bringing the absorbent in the absorbent storage unit into contact with the exhaust gas oxidized in the gas phase reaction unit.
In a preferred embodiment of the present application, the gas phase reaction unit is a pipe or a reactor for transporting exhaust gas.
In a preferred embodiment of the present application, the alkaline earth metal compound is selected from the group consisting of calcium carbonate, calcium hydroxide, and mixtures thereof.
In a preferred embodiment of the present application, the organic acid is selected from the group consisting of RCOOH (r=h or an alkyl group having 1 to 18 carbon atoms), a dicarboxylic acid having 1 to 20 carbon atoms, and a mixture thereof.
In a preferred embodiment of the present application, the gas phase reaction unitComprising the following steps: oxidizing Nitric Oxide (NO) contained in the exhaust gas into nitrogen dioxide (NO) by reacting the exhaust gas with ozone 2 )。
In a preferred embodiment of the present application, the desulfurization in the wet reaction section is a desulfurization reaction performed by a reaction between an alkaline earth metal compound in the absorbent and an oxide of sulfur in the exhaust gas. The denitrification in the wet reaction section is nitrogen dioxide (NO) obtained by reacting an alkaline earth metal sulfite formed by a desulfurization reaction of an alkaline earth metal compound in an absorbent with Nitric Oxide (NO) and ozone contained in an exhaust gas in the gas phase reaction section 2 ) Is carried out by the reaction of the catalyst.
In another preferred embodiment of the present application, the above gas phase reaction part includes a grid nozzle for injecting ozone so as to sufficiently mix the exhaust gas and ozone.
In another preferred embodiment of the present application, the wet reaction section is an absorber used in a flue gas desulfurization apparatus in a thermal power plant, and the absorber is sprayed with the absorbent supplied from the absorbent storage section, and the sprayed absorbent is brought into contact with the exhaust gas oxidized in the gas phase reaction section, thereby denitrifying and desulfurizing the exhaust gas containing sulfur oxides and nitrogen oxides.
Effects of the application
According to the present application, the denitrification process of the exhaust gas is performed by the wet process under the same operation conditions as the desulfurization process, not only the denitrification process and the desulfurization process of the exhaust gas can be simultaneously performed on one wet process equipment (wet flue gas desulfurization device), but also the denitrification and the desulfurization can be performed without changing or adding the equipment for denitrification in the existing wet process operation, thereby having the effect of reducing the inefficiency and the side effects occurring when different operation conditions are respectively applied to the denitrification process and the desulfurization process while being economical.
In addition, according to the present application, nitric Oxide (NO) of the exhaust gas having low reactivity is converted into nitrogen dioxide (NO) having high reactivity by ozone 2 ) And increased by the addition of organic acids or organic acid saltsThe intermediate product of sulfur oxide produced at this time is used as a denitrification agent while adding the reaction rate of sulfur oxide and absorbent in the exhaust gas, so that the addition of expensive denitrification additives (Na 2 S、Na 2 SO 3 ) Therefore, the method has the effect of realizing high denitrification and desulfurization efficiency of the waste gas.
Drawings
Fig. 1 is a schematic diagram of simultaneous removal of sulfur oxides and nitrogen oxides from exhaust gas according to an embodiment of the application.
Fig. 2 is a schematic diagram of simultaneous removal of sulfur oxides and nitrogen oxides from exhaust gas according to another embodiment of the application.
Fig. 3 is a block diagram of simultaneous removal of sulfur oxides and nitrogen oxides from exhaust gas according to an embodiment of the present application.
Reference numerals illustrate:
10: a gas phase reaction section; 11: a mass flowmeter; 15: an air duct; 20: an absorbent storage section;
21. 33: a pipe; 22: a storage tank; 23. 32: a stirring unit;
30: a wet reaction section; 31: a wet process reactor; 35: an absorption tower.
Detailed Description
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art. Generally, the nomenclature used in this specification is that well known and commonly employed in the art.
In the entire specification of the present application, a certain component "comprising" means that other components may be included without excluding other components unless expressly stated to the contrary.
The present application relates to a method for simultaneously removing sulfur oxides and nitrogen oxides contained in exhaust gas, which comprises the following steps: (a) A step of oxidizing nitrogen oxides contained in the exhaust gas by reacting the exhaust gas with ozone; (b) A step of obtaining an absorbent by mixing an organic acid or an organic acid salt in an alkaline earth metal compound in an aqueous solution state or a slurry state; and (c) a step of bringing the exhaust gas oxidized by the reaction with ozone in the step (a) into contact with the absorbent in the step (b) to thereby denitrify and desulfurize the exhaust gas.
In addition, the present application relates to an apparatus for simultaneously removing sulfur oxides and nitrogen oxides contained in exhaust gas, comprising: a gas phase reaction unit that oxidizes nitrogen oxides contained in the exhaust gas by reacting the exhaust gas with ozone; an absorbent storage unit for storing an absorbent by mixing an organic acid or an organic acid salt with an alkaline earth metal compound in an aqueous solution state or a slurry state; and a wet reaction unit configured to denitrify and desulphurize exhaust gas containing sulfur oxides and nitrogen oxides by bringing the absorbent in the absorbent storage unit into contact with the exhaust gas oxidized in the gas phase reaction unit.
In particular, the method and apparatus for simultaneously removing sulfur oxides and nitrogen oxides contained in exhaust gas according to the present application relates to a method and apparatus for accomplishing not only desulfurization of sulfur oxides but also denitrification of nitrogen oxides by using a wet desulfurization process for removing sulfur oxides contained in exhaust gas, which can simultaneously perform a denitrification process and a desulfurization process of exhaust gas by one wet treatment process and can simultaneously treat sulfur oxides and nitrogen oxides with economy without changing equipment for denitrification or adding expensive denitrification additives in the existing operating wet desulfurization process.
Hereinafter, a method and apparatus for simultaneously removing sulfur oxides and nitrogen oxides contained in exhaust gas according to the present application will be described in detail with reference to the accompanying drawings and according to the steps.
FIG. 1 is a schematic illustration of simultaneous removal of sulfur oxides and nitrogen oxides from exhaust gas in accordance with an embodiment of the present application; FIG. 2 is a schematic illustration of simultaneous removal of sulfur oxides and nitrogen oxides from exhaust gas in accordance with another embodiment of the application; fig. 3 is a block diagram of simultaneous removal of sulfur oxides and nitrogen oxides from exhaust gas according to an embodiment of the present application.
According to the application, sulfur Oxides (SO) contained in the exhaust gas are removed simultaneously x ) And Nitrogen Oxides (NO) x ) Is a device package of (a)The method comprises the following steps: a gas phase reaction section 10, an absorbent storage section 20, and a wet process reaction section 30.
The gas phase reaction unit 10 is provided between an exhaust gas generation source (not shown) and the wet process reaction unit 30. The exhaust gas discharged from the exhaust gas generating source is supplied to the gas phase reaction section 10, and then supplied to the wet process reaction section 30 through the gas phase reaction section 10.
The gas phase reaction unit 10 reacts the exhaust gas with ozone to convert Nitrogen Oxides (NO) contained in the exhaust gas x ) Oxidation is performed [ step (a) ].
Nitrogen Oxides (NO) contained in the exhaust gas x ) Most consists of Nitric Oxide (NO) which is less reactive and soluble and more difficult to wet process. In the present application, nitrogen monoxide (NO) in such nitrogen oxides is converted into highly reactive and soluble and wet-treatable nitrogen dioxide (NO) by selective oxidation reaction with ozone 2 ) Thus, the denitrification process in the wet reaction section 30 described later can be performed, and the effect of the present application can be improved.
For example, through the above step (a), nitric Oxide (NO) contained in the exhaust gas can be converted into nitrogen dioxide (NO) according to the following reaction formula 1 2 )。
[ reaction type 1 ]
NO(g)+O 3 →NO 2 (g)+O 2
At this time, the exhaust gas and ozone may be injected into the gas phase reaction section 10 by adjusting the flow rate by the mass flowmeter 11 or the like. The gas phase reaction part 10 may use a duct (duct) 15 for transporting exhaust gas, a teflon tube reactor 12, or the like, but is not limited thereto. The gas residence time in the reactor may be changed by changing the length of the reactor using the above-mentioned tube, the gas residence time in the gas phase reaction part may be changed, and the gas residence time in the gas phase reaction part is proportional to the volume of the reactor, and thus may be preferably 2 seconds to 10 seconds, but is not limited thereto.
In the present application, in order to sufficiently mix the exhaust gas and ozone, the gas phase reaction unit 10 includes a grid nozzle (not shown) for injecting ozone, and as shown in fig. 1, the nozzle is provided in a step preceding the wet reaction unit.
Wherein the reaction conditions in the gas phase reaction section 10 are 160 ℃ or less, and the exhaust gas and ozone are preferably reacted at 130 ℃ or less. Since the molar ratio of ozone to nitrogen oxide reacts with nitrogen oxide in an equivalent manner, ozone may be injected in an equivalent amount in order to remove nitrogen oxide. If an excessive amount of ozone is used, ozone is discharged to the atmosphere to cause pollution, and therefore, the equivalent ratio of ozone to nitrogen oxides is preferably 1 or less.
On the one hand, the absorbent storage section 20 stores an absorbent obtained by mixing an organic acid or an organic acid salt with an alkaline earth metal compound in an aqueous solution state or a slurry state, and supplies the stored absorbent to the wet reaction section 30 where denitrification and desulfurization are performed [ step b ].
The absorbent storage unit 20 may be connected to the wet reaction unit through a connection pipe 21. The above-described connection pipe 21 has one side connected to the absorbent storage part 20 and the other side connected to the wet reaction part 30, so that the absorbent stored in the absorbent storage part 20 can be supplied to the wet reaction part 30 through the connection pipe, and may further include a pump, a valve, etc. for use therein.
The above-mentioned absorbent can be prepared by mixing an organic acid or an organic acid salt with an alkaline earth metal compound in the form of an aqueous solution or slurry in which the alkaline earth metal compound is dispersed in water. In this case, the above-mentioned mixing can be easily performed by a method used in the art.
The alkaline earth metal compound may be one or more selected from the group consisting of calcium carbonate and calcium hydroxide, and calcium carbonate is preferable in terms of treatment cost and practicality.
In one aspect, the organic acid is selected from the group consisting of RCOOH (r=h or alkyl of 1 to 18 carbon atoms), dicarboxylic acids of 1 to 20 carbon atoms, and mixtures thereof, preferably formic acid, and the organic acid salt is preferably an alkaline earth metal salt of formic acid.
The absorbent of the present application as described above is prepared by mixing an organic acid or an organic acid salt with an alkaline earth metal compound, and the ion exchange reaction by the organic acid is carried out on the surface of the alkaline earth metal compound, so that the surface of the alkaline earth metal compound is continuously consumed, and the particle size of the absorbent can be made smaller.
This principle is very similar to CMP of semiconductor processes and the etching rate of the calcium carbonate surface depends on the acid content and the degree of particle movement. Although the higher the acid content or the greater the particle movement, the smaller the particle size, it is sufficient to determine its extent on the COD and cost limits of the wastewater.
In addition, the solubility of alkaline earth metal compounds in water is generally very low, and thus has a problem of very low reactivity with sulfur oxides and nitrogen oxides caused in an aqueous phase. This problem can be solved by adding an organic acid because an alkali metal salt such as a calcium salt that enhances water solubility can be formed by the reaction of an alkaline earth metal compound with the organic acid. That is, since sulfur oxides can only react with calcium in the aqueous phase, the higher the concentration of calcium salt soluble in water in the wet process, the more calcium ions come into contact with sulfur oxides and sulfur oxides can be effectively removed.
In particular, when formic acid is used as the above-mentioned organic acid, a sufficient effect can be obtained with a smaller amount of the organic acid due to the lower molecular weight of formic acid, and corrosion and/or erosion in the device can be prevented while minimizing the increase in COD.
In general, in order to promote removal of sulfur oxides in exhaust gas, a considerable amount of dibasic acid (dibasic acid) or the like needs to be continuously added to maintain a sufficient concentration in a liquid phase, but it is known that such an excessive amount of dibasic acid or the like can promote corrosion and/or erosion in the apparatus over a long period of time, and further COD problems may occur. That is, when COD is increased, there is a disadvantage in that the wastewater process needs to be performed again to remove it.
However, formic acid has a half carbon number of dibasic acid and excellent physicochemical properties of water solubility compared with dibasic acid, so that the particle size of the absorbent can be greatly reduced when it is mixed with the absorbent. In addition, by producing an alkali metal salt having improved solubility, not only desulfurization and denitrification efficiency can be improved, but also safety problems and environmental problems in the conventional desulfurization and denitrification processes to which dibasic acids are applied as organic acids can be solved.
In particular, in the present application, when the carbon number of the adsorbent is dibasic acid (e.g., HOOC-CH 2 -CH 2 -COOH) as an additive, not only an alkali metal salt excellent in water solubility can be produced, but also the reactivity and absorptivity of sulfur oxides and nitrogen oxides in exhaust gas can be further improved as the surface of the absorbent is consumed by the ion exchange reaction with the surface of the alkaline earth metal compound, and the particle size of the absorbent becomes smaller.
In the present application, the organic acid or organic acid salt contained in the absorbent is 1ppm to 3000ppm, preferably 10ppm to 2000ppm, relative to the solid content of the absorbent.
If the organic acid or organic acid salt is mixed so as to be less than 1ppm relative to the solid content, the effect of mixing the organic acid or organic acid salt cannot be exerted, and if it exceeds 3000ppm, the cost increases and problems such as COD and corrosion may occur.
In addition, in the present application, in order to promote dissolution of calcium in the absorbent, and further in order to promote desulfurization and denitrification, the absorbent containing the above-mentioned organic acid may include an additional organic acid including an organic acid containing only carboxyl groups (e.g., acetic acid, propionic acid, butyl carboxylic acid, amyl carboxylic acid, adipic acid, succinic acid, maleic acid, malic acid, etc.) or an organic acid containing both carboxyl groups and hydroxyl groups, such as 3-hydroxypropionic acid, glycolic acid, etc., in addition to formic acid. Wherein the organic acid containing both carboxyl and hydroxyl groups may be a polymer or a single molecule.
The absorbent storage unit 20 may include a storage tank 22 and a stirring unit 23. The storage tank 22 for storing the absorbent may store the absorbent in an aqueous solution state or a slurry state. The storage tank 22 may be connected to the wet reaction section 30 through a connection pipe 21.
The stirring unit 23 provided in the storage tank 22 stirs the absorbent stored in the storage tank 22 to be uniform, thereby promoting the reaction between the organic acid or the organic acid salt and the alkaline earth metal compound.
As described above, the absorbent in the absorbent storage part 20 and the exhaust gas oxidized in the gas phase reaction part 10 are supplied to the wet reaction part 30, and the exhaust gas supplied to the above wet reaction part 30 is contacted with the absorbent in the wet reaction part, thereby performing denitrification and desulfurization of the exhaust gas [ step (c) ].
In the wet reaction section 30, desulfurization is performed by a reaction between the sulfur oxide of the exhaust gas and the alkaline earth metal compound in the absorbent; by alkaline earth metal sulphites (SO 3 2- ) And nitrogen dioxide generated by oxidizing and absorbing nitrogen monoxide in the exhaust gas, wherein the alkaline earth metal sulfite is an intermediate product generated by a desulfurization reaction between an oxide of sulfur in the exhaust gas and an alkaline earth metal compound in the absorbent.
In one example, desulfurization in the wet reaction section 30 is achieved by: the sulfur oxides of the exhaust gas are absorbed in the injected limestone slurry in the process of passing the sulfur oxides of the exhaust gas through the liquid phase reactor or the absorption tower of the flue gas desulfurization device in the thermal power plant and the like.
On the other hand, in the case where the absorbent containing calcium carbonate is supplied from the above-described absorbent storage section to the wet reaction section, desulfurization and denitrification reactions can be performed according to the following equations 2 to 7.
[ reaction type 2 ]
(parallel reaction, slow reaction)
[ reaction type 3 ]
CaCO 3 (s)+2H + →Ca 2+ +H 2 O+CO 2 (g) (slow)
[ reaction type 4 ]
CaCO 3 (s)+2RCOOH(l)→Ca(RCOO) 2 (l)+H 2 O+CO 2 (fast)
[ reaction type 5 ]
Ca(RCOO) 2 (l)+2H + →Ca 2+ +2RCOOH (l) (fast)
[ reaction type 6 ]
Ca 2+ +SO 3 2- (l)→CaSO 3 (S) (fast)
[ reaction type 7 ]
CaSO 3 (s)+1/2NO 2 →CaSO 4 (s)+1/4N 2 (fast)
As shown in the above equations 2 to 7, sulfur dioxide (SO) in the exhaust gas supplied from the gas phase reaction section 10 2 ) Reacts with water in the absorbent to generate hydrogen ions and sulfite ions, and the generated hydrogen ions (protons) react with calcium carbonate of the absorbent to generate calcium ions. However, the reaction rate of calcium ions generated therein is slow, and thus the completeness of desulfurization and decarburization reactions is limited.
Thus, as in the present application, when an organic acid or an organic acid salt is added, calcium ions can be rapidly generated according to equations 4 and 5. The calcium ions generated in this way react with the previously generated sulfite ions according to equation 6 to generate calcium sulfite (CaSO 3 ). The calcium sulfite produced at this time reacts with nitrogen dioxide previously produced in the gas phase reaction section, whereby the above calcium sulfite is changed into calcium sulfate, and the nitrogen dioxide is converted into nitrogen to perform the denitrification reaction.
On the one hand, the desulfurization is carried out by passing sulfur dioxide contained in the exhaust gas through sulfite ions (SO 3 2- ) The final conversion to calcium sulfate (calcium salt) is achieved and is thereby removed from the exhaust gas.
That is, as shown in reaction formula 7, calcium sulfite (CaSO) produced by desulfurization of sulfur dioxide 3 ) Is used as a reducing agent for nitrogen oxides and is produced by the above-mentioned calcium sulfite (CaSO 3 ) Reaction with Nitrogen dioxideNitrogen (N) generation 2 ) And calcium sulfate (CaSO) 4 ). The process according to the application is therefore technically characterized in that in the case of calcium carbonate containing an organic acid, this calcium sulfite, which can be produced by the desulfurization reaction, can react more rapidly and be used for denitrification, whereby nitrogen dioxide in the exhaust gas is converted into nitrogen (N 2 ) Is removed from the exhaust gas.
As a result, the organic acid or organic acid salt mixed in the absorbent not only absorbs sulfur oxides but also enhances absorption of nitrogen oxides, and at the same time, the reaction rate of the slow reactions of equations 2 and 3 can be accelerated by the catalytic action of equations 4 to 5, as a result of which the above-mentioned organic acid or organic acid salt can play a decisive role in generating more calcium sulfite.
In this case, in order to increase the denitrification efficiency of the exhaust gas, it is necessary to increase the concentration of calcium sulfite as a reducing agent. For this purpose, it is necessary to increase the desulfurization rate, and therefore, in the present application, expensive denitrification additives (Na 2 S、Na 2 SO 3 Etc.), the nitrogen removal and desulfurization efficiency of the exhaust gas can be maximized by using an absorbent mixed with an organic acid or an organic acid salt.
The wet reaction part 30 according to the present application may include a wet reactor 31 and a stirring unit 32. As described above, sulfur oxides and nitrogen oxides are absorbed by limestone slurry injected during passage through the absorption tower 35 of a flue gas desulfurization apparatus at a thermal power plant or the like, and thus desulfurization and denitrification can be performed simultaneously.
The above-described matters can be described in detail with reference to fig. 2, and fig. 2 shows a specific example in which the desulfurization and denitrification reaction according to the present application can be performed in a flue gas desulfurization apparatus in a conventional thermal power plant. As a device corresponding to the above-described gas phase reaction section in the present application, an exhaust gas conveying duct for conveying exhaust gas is used. Ozone generated from the ozone generating part in the air duct and Nitrogen Oxides (NO) x ) In particular Nitric Oxide (NO), to convert said nitric oxide into nitrogen dioxide (NO) 2 ) And go throughThe product of the oxidation reaction of nitrogen oxides by ozone (containing nitrogen dioxide (NO 2 ) Is passed through an absorber 35 in the existing flue gas desulfurization apparatus. The slurry supplied from the absorbent storage unit 20 in the absorber is sprayed in a direction from above to below, and as a result, the sprayed liquid falls downward due to gravity, wherein the absorbent storage unit 20 contains limestone slurry used for the conventional desulfurization reaction. At this time, the injected slurry reacts with the product of the oxidation reaction of nitrogen oxides by the ozone (containing nitrogen dioxide (NO 2 ) A mixed gas of (c) and (d) is reacted, an apparatus for simultaneously performing desulfurization and denitrification is shown in fig. 2.
That is, the wet reaction section in the present application corresponds to an absorption tower used in a flue gas desulfurization apparatus in a thermal power plant, and the desulfurization and denitrification apparatus may be configured by injecting the absorbent of the present application supplied from the absorbent storage section into the absorption tower so that the injected absorbent contacts the exhaust gas oxidized from the gas reaction section according to the present application, thereby denitrifying and desulfurizing the exhaust gas containing sulfur oxides and nitrogen oxides.
Accordingly, the present application uses the slurry injection device and the exhaust gas transfer duct used in the prior art as they are, and uses the exhaust gas transfer duct as a gas phase reaction part, thereby further utilizing the exhaust gas transfer duct in an oxidation reaction with ozone. In addition, by adding only the alkaline earth metal compound in the form of an aqueous solution or slurry to the absorbent storage unit and mixing the alkaline earth metal compound with an organic acid or an organic acid salt and using the mixture as an absorbent, it is possible to achieve an excellent effect that the denitrification reaction can be further performed in addition to the desulfurization reaction alone in the conventional absorption tower.
On the other hand, in the case where the above-mentioned wet reactor according to the present application includes the wet reactor 31 and the stirring unit 32 instead of the absorption tower system at the place of the thermal power generation station of the related art or the like, there may be formed: each inflow port (not shown) through which the absorbent and the exhaust gas can flow, respectively; a reaction unit (not shown) in which denitrification and desulfurization of the absorbent and the exhaust gas can be performed; and a discharge port for discharging the denitrification and desulfurization products. Further, since the stirring unit 32 is provided in the wet reactor 31, the absorbent and the exhaust gas supplied to the wet reaction section are stirred to promote denitrification and desulfurization of the exhaust gas. In this case, the stirring unit 32 may be used without limitation as long as it is a member for improving the gas-liquid contact efficiency between the absorbent and the exhaust gas; the stirring unit 32 may be a stirrer, a bubble generator (bubble generator), or the like.
After that, the above exhaust gas is discharged to the outside through the connection duct 33 after removing nitrogen oxides and sulfur oxides by desulfurization and denitrification processes in the wet reaction part. At this time, the alkali metal salt generated in the wet reaction section remains in the wet reaction section in the form of an aqueous solution or slurry, and can be recovered for use by obtaining calcium sulfate (gypsum) or discharging to a treatment facility (not shown).
According to the method and apparatus for simultaneously removing sulfur oxides and nitrogen oxides contained in exhaust gas of the present application, nitrogen monoxide having low reactivity is converted into nitrogen dioxide having high reactivity through reaction with ozone, and then the denitrification process is performed in parallel under the same conditions as the desulfurization process by supplying an absorbent in the state of an aqueous solution or slurry containing an organic acid or an organic acid salt, so that inefficiency and side effects occurring when different operation conditions are applied to the denitrification process and the desulfurization process, respectively, can be reduced, and residual nitrogen oxides which cannot be removed in the selective catalytic reduction apparatus can be effectively removed while improving desulfurization performance by applying existing wet desulfurization equipment in situ without adding expensive denitrification additives.
Hereinafter, the present application will be described more specifically by way of examples of the present application. However, the following embodiment is merely an example of the present application, and the scope of the present application is not limited to the following embodiment.
< examples 1 to 2>
Waste gas of Korean coal thermal power plant A (example 1) and B (example 2) was sampled and an equal amount of 14p was injected into a waste gas sampling line having a length of 10mpm ozone, by measuring the conversion of Nitric Oxide (NO) to nitrogen dioxide (NO) 2 ) And is shown in table 1.
TABLE 1
| Partitioning | NO(ppm) | NO 2 (ppm) | Conversion (%) |
| Example 1 | 14 | 14 | 100 |
| Example 2 | 25 | 25 | 100 |
As shown in table 1, it was confirmed that the oxidation reaction of nitric oxide by ozone completely converted nitric oxide into nitrogen dioxide.
< examples 3 to 7>
The flue gas containing nitrogen oxides and sulfur oxides is subjected to denitrification and desulfurization using the apparatus shown in fig. 2.
First, a mass flow meter was used to obtain a mixture containing 13ppm of Nitric Oxide (NO) and 425ppm of sulfur dioxide (SO 2 ) Is mixed with 4.5g/m of waste gas 3 Ozone of 4.8m 3 And/hr is injected into the gas phase reaction part 10. Ozone and one of the aboveThe molar ratio of nitrogen oxide is the equivalence ratio.
The exhaust gas and ozone remain in the gas phase reaction section for 6.2 seconds, and the exhaust gas is oxidized by reaction with ozone at normal temperature and normal pressure. The oxidized waste gas is in a volume of 4.8m 3 The reaction mixture was supplied to the wet reaction section 30 in the manner of/hr, reacted with an absorbent and the removal rates of nitrogen oxides and sulfur oxides were measured by a combustible gas detector (testo 350) and are shown in table 2.
At this time, an absorbent was prepared by adding the organic acid and the content of table 2 to the calcium carbonate slurry of 20% solid content, and the absorbent prepared above was supplied to the wet reaction section (100L) in a volume of 50L. In this case, the above-mentioned absorbent used an absorbent which passes 325 mesh at 90%.
Comparative examples 1 to3 ]
The nitrogen oxides and sulfur oxides contained in the exhaust gas were removed by the same method as in example 1, and the nitrogen oxides and sulfur oxides of the exhaust gas were removed by the conditions of table 2, and the removal rates of the nitrogen oxides and sulfur oxides were measured using a flammable gas detector and are shown in table 2.
TABLE 2
As shown in table 2, it was confirmed that the removal rates of nitrogen oxides and sulfur oxides in examples 3 to 7 were far higher than those in comparative examples 1 and 2, and in particular, the removal rate of nitrogen oxides of 90% or more was shown in the case of mixing formic acid of 1000ppm or more in organic acids. Further, as shown in comparative example 1, it was confirmed that the removal rate of nitrogen oxides was 50% or more even in the case where the organic acid was not mixed, but the removal rates of nitrogen oxides and sulfur oxides were higher when the organic acid was properly used. In the case of comparative example 3, although the removal rates of nitrogen oxides and sulfur oxides are high, side effects of increasing the treatment cost and COD of desulfurization wastewater are generated.
The specific parts of the present application have been described in detail above, and are not limited to what is illustrated in the accompanying drawings, but it is obvious to those skilled in the art that the above-described specific techniques are merely preferred embodiments, and the scope of the present application is not limited thereto. Therefore, the actual scope of the application should be defined by the appended claims and equivalents thereof.
Claims (6)
1. A method for simultaneously removing sulfur oxides and nitrogen oxides contained in exhaust gas, comprising:
a step (a) of oxidizing nitrogen oxides contained in the exhaust gas by reacting the exhaust gas with ozone;
a step (b) of obtaining an absorbent by mixing an organic acid or an organic acid salt in an alkaline earth metal compound in an aqueous solution state or a slurry state; a kind of electronic device with high-pressure air-conditioning system
A step (c) of performing denitrification and desulfurization of the exhaust gas by contacting the exhaust gas oxidized by the reaction with ozone in the step (a) with the absorbent of the step (b),
the desulfurization in the step (c) is a desulfurization reaction performed by a reaction of sulfur oxides of exhaust gas and alkaline earth metal compounds in the absorbent,
the denitrification of the step (c) is a denitrification reaction in which nitrogen dioxide is converted into nitrogen by a reaction of an alkaline earth metal sulfite, which is generated by a desulfurization reaction of an sulfur oxide of an exhaust gas and an alkaline earth metal compound in which an organic acid or an organic acid salt is mixed in an absorbent, with nitrogen dioxide obtained by a reaction of nitric oxide contained in the exhaust gas with ozone in the step (a),
the alkaline earth metal compound of step (b) is selected from the group consisting of calcium carbonate, calcium hydroxide and mixtures thereof,
the organic acid of step (b) is selected from the group consisting of RCOOH, a dicarboxylic acid having 1 to 20 carbon atoms, and mixtures thereof; wherein R in RCOOH is H or alkyl with 1-18 carbon atoms.
2. A method for simultaneously removing sulfur oxides and nitrogen oxides contained in exhaust gas as claimed in claim 1,
the content of the organic acid or organic acid salt in the step (b) is 1ppm to 3000ppm relative to the solid content in the absorbent.
3. An apparatus for simultaneously removing sulfur oxides and nitrogen oxides contained in exhaust gas, comprising:
a gas phase reaction unit that oxidizes nitrogen oxides contained in the exhaust gas by reacting the exhaust gas with ozone;
an absorbent storage unit that stores an absorbent obtained by mixing an organic acid or an organic acid salt with an alkaline earth metal compound in an aqueous solution state or a slurry state; a kind of electronic device with high-pressure air-conditioning system
A wet reaction section for denitrifying and desulfurizing the exhaust gas containing sulfur oxides and nitrogen oxides by bringing the absorbent in the absorbent storage section into contact with the exhaust gas oxidized in the gas phase reaction section,
the desulfurization in the wet reaction section is a desulfurization reaction performed by a reaction of an alkaline earth metal compound in the absorbent with an oxide of sulfur of the exhaust gas,
the denitrification in the wet reaction section is a denitrification reaction in which nitrogen dioxide is converted into nitrogen by a reaction of an alkaline earth metal sulfite, which is produced by a desulfurization reaction of an alkaline earth metal compound in which an organic acid or an organic acid salt is mixed in an absorber and an sulfur oxide of an exhaust gas, with nitrogen dioxide obtained by a reaction of nitric oxide contained in the exhaust gas with ozone in the gas phase reaction section,
the alkaline earth metal compound is selected from the group consisting of calcium carbonate, calcium hydroxide, and mixtures thereof,
the organic acid is selected from the group consisting of RCOOH, a dicarboxylic acid having 1 to 20 carbon atoms, and mixtures thereof; wherein R in RCOOH is H or alkyl with 1-18 carbon atoms.
4. The apparatus for simultaneously removing sulfur oxides and nitrogen oxides contained in exhaust gas as claimed in claim 3, wherein,
the gas phase reaction part is an air duct or a reactor for conveying waste gas.
5. The apparatus for simultaneously removing sulfur oxides and nitrogen oxides contained in exhaust gas as claimed in claim 3, wherein,
the gas phase reaction part includes a grid nozzle for injecting ozone for sufficiently mixing exhaust gas and ozone, the nozzle being disposed at a step before the wet reaction part.
6. The apparatus for simultaneously removing sulfur oxides and nitrogen oxides contained in exhaust gas as claimed in claim 3, wherein,
the wet reaction section is an absorption tower used in a flue gas desulfurization apparatus in a thermal power plant, and an absorbent supplied from the absorbent storage section (20) is injected into the absorption tower, and the injected absorbent contacts the exhaust gas oxidized in the gas phase reaction section, thereby denitrifying and desulfurizing the exhaust gas containing sulfur oxides and nitrogen oxides.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020190042045A KR102198314B1 (en) | 2019-04-10 | 2019-04-10 | Method and Apparatus for Simultaneous Removal of SOx and NOx in the Flue Gas |
| KR10-2019-0042045 | 2019-04-10 | ||
| PCT/KR2020/004776 WO2020209611A1 (en) | 2019-04-10 | 2020-04-08 | Method and apparatus for simultaneously removing sulfur oxide and nitrogen oxide contained in exhaust gas |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113677421A CN113677421A (en) | 2021-11-19 |
| CN113677421B true CN113677421B (en) | 2023-09-12 |
Family
ID=72752108
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202080027806.3A Active CN113677421B (en) | 2019-04-10 | 2020-04-08 | Method and device for simultaneously removing sulfur oxides and nitrogen oxides contained in exhaust gas |
Country Status (3)
| Country | Link |
|---|---|
| KR (1) | KR102198314B1 (en) |
| CN (1) | CN113677421B (en) |
| WO (1) | WO2020209611A1 (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1923341A (en) * | 2006-08-23 | 2007-03-07 | 浙江大学 | Device and method for coal-burning boiler fume ozone oxidation and simultaneous desulfurization and denitrification |
| JP2009166012A (en) * | 2008-01-21 | 2009-07-30 | Mitsubishi Heavy Ind Ltd | Exhaust gas treatment system and its operation method of coal fired boiler |
| KR20180071804A (en) * | 2016-12-20 | 2018-06-28 | 디에스티주식회사 | Method for Adjusting Particle Size of Alkaline Wet Flue Gas Desulfurizing Agent and Method for Wet Flue Gas Desulfurization Using the Same |
| KR101876413B1 (en) * | 2017-04-20 | 2018-07-09 | 케이씨코트렐 주식회사 | FLUE GAS TREATMENT APPARATUS FOR REMOVING NOx and SOx SIMULTANEOUSLY |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4616497B2 (en) * | 2001-04-04 | 2011-01-19 | 大阪瓦斯株式会社 | Desulfurization apparatus and desulfurization method |
| CN105214457B (en) | 2014-06-05 | 2018-04-17 | 魏雄辉 | A kind of fume desulfuring and denitrifying Processes and apparatus |
| KR101519900B1 (en) * | 2014-11-26 | 2015-05-18 | 주식회사 정원이앤씨 | DeSOx and DeNOx system for plant |
| KR101551806B1 (en) * | 2015-01-20 | 2015-09-09 | 주식회사 정원이앤씨 | DeSOx and DeNOx system for ship |
| KR101724358B1 (en) | 2015-08-28 | 2017-04-10 | 인하대학교 산학협력단 | Method for the Simultaneous Removal of Nitrogen Oxides and Sulfur Dioxide using Ozone Oxidation and Wet Scrubber |
| KR101800517B1 (en) | 2015-12-30 | 2017-11-23 | 주식회사 포스코아이씨티 | Wet-type Apparatus and Method for Removing Harmful Substance from Exhaust Gas |
-
2019
- 2019-04-10 KR KR1020190042045A patent/KR102198314B1/en active IP Right Grant
-
2020
- 2020-04-08 CN CN202080027806.3A patent/CN113677421B/en active Active
- 2020-04-08 WO PCT/KR2020/004776 patent/WO2020209611A1/en active Application Filing
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1923341A (en) * | 2006-08-23 | 2007-03-07 | 浙江大学 | Device and method for coal-burning boiler fume ozone oxidation and simultaneous desulfurization and denitrification |
| JP2009166012A (en) * | 2008-01-21 | 2009-07-30 | Mitsubishi Heavy Ind Ltd | Exhaust gas treatment system and its operation method of coal fired boiler |
| KR20180071804A (en) * | 2016-12-20 | 2018-06-28 | 디에스티주식회사 | Method for Adjusting Particle Size of Alkaline Wet Flue Gas Desulfurizing Agent and Method for Wet Flue Gas Desulfurization Using the Same |
| KR101876413B1 (en) * | 2017-04-20 | 2018-07-09 | 케이씨코트렐 주식회사 | FLUE GAS TREATMENT APPARATUS FOR REMOVING NOx and SOx SIMULTANEOUSLY |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2020209611A1 (en) | 2020-10-15 |
| KR20200119617A (en) | 2020-10-20 |
| CN113677421A (en) | 2021-11-19 |
| KR102198314B1 (en) | 2021-01-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110075702B (en) | Device for simultaneously removing nitrogen oxides (NOx) and sulfur oxides (SOx) in exhaust gas | |
| AU768213B2 (en) | Process for removing NOx and SOx from exhaust gas | |
| CN102343212B (en) | Denitration process combining co-oxidation of ozone and hydrogen peroxide with wet absorption | |
| CN1087964C (en) | Method and apparatus for treating waste gases by exposure to electron beams | |
| CN103480251B (en) | System and method for performing desulfurization, denitration and demercuration to flue gas simultaneously | |
| CN115996785B (en) | Improved method and device for simultaneously removing sulfur oxides and nitrogen oxides contained in exhaust gas | |
| KR101800517B1 (en) | Wet-type Apparatus and Method for Removing Harmful Substance from Exhaust Gas | |
| CN104587809B (en) | A kind of desulfurizing and denitrifying process of ozone hydroxyl radical free radical dry-and-wet combined | |
| CN110787606B (en) | Denitration and demercuration integrated device and method for sintering flue gas circulating fluidized bed desulfurization | |
| CN101637688B (en) | Treatment method and device for waste gas containing nitrogen oxides | |
| CN102847418A (en) | Additive for limestone-gypsum wet flue gas desulfurization and denitration process | |
| Guo et al. | Simultaneous removal of SO2 and NOx with ammonia combined with gas-phase oxidation of NO using ozone | |
| CN113677421B (en) | Method and device for simultaneously removing sulfur oxides and nitrogen oxides contained in exhaust gas | |
| KR20200072373A (en) | manufacturing method of liquid catalyst compositions for desulfurization and pre-treatment apparatus of bio gas | |
| CN206762618U (en) | A kind of dry-wet integratedization desulfuring and denitrifying apparatus | |
| KR102134129B1 (en) | ACTIVATED CARBON FOR REDUCTION OF Fe(Ⅲ)-EDTA AND REGENERATION OF Fe(Ⅱ)-EDTA-NO, AND THE PROCESS USING Fe(Ⅱ)-EDTA FOR REMOVING NITROGEN OXIDE AND SULFUR OXIDE | |
| CN205570056U (en) | Device of low temperature flue gas desulfurization denitration integration | |
| CN106853329A (en) | Ozone for low-temperature denitration of flue gas generates the method and device of hydroxyl radical free radical | |
| KR100531767B1 (en) | H2S Gas Exclusion Method and The Apparatus of Coke Oven Gas | |
| CN206334533U (en) | A kind of desulphurization denitration uphole steam generator | |
| CN111744330A (en) | Desulfurization and denitrification cooperative absorption integrated equipment and method | |
| CN207641256U (en) | A kind of auxiliary denitrating system suitable for the coal-burning boiler start and stop stage | |
| CN110876885A (en) | Flue gas desulfurization and denitrification system and method based on ozone-assisted catalytic oxidation | |
| CN105214456A (en) | A kind of SNCR-SCR flue-gas denitration process | |
| Jia et al. | Preparation of ozone for simultaneous removal of SO2 and NO x with mud-phosphorus slurry |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |