WO2022075506A1 - Procédé et appareil améliorés pour l'élimination simultanée de l'oxyde de soufre et de l'oxyde d'azote contenus dans un gaz d'échappement - Google Patents

Procédé et appareil améliorés pour l'élimination simultanée de l'oxyde de soufre et de l'oxyde d'azote contenus dans un gaz d'échappement Download PDF

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WO2022075506A1
WO2022075506A1 PCT/KR2020/013878 KR2020013878W WO2022075506A1 WO 2022075506 A1 WO2022075506 A1 WO 2022075506A1 KR 2020013878 W KR2020013878 W KR 2020013878W WO 2022075506 A1 WO2022075506 A1 WO 2022075506A1
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exhaust gas
absorbent
nitrogen
desulfurization
reaction unit
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PCT/KR2020/013878
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English (en)
Korean (ko)
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유해윤
조상제
윤대성
석동규
임태현
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디에스티주식회사
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Priority to CN202080105160.6A priority Critical patent/CN115996785B/zh
Publication of WO2022075506A1 publication Critical patent/WO2022075506A1/fr

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    • 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
    • B01D47/00—Separating dispersed particles from gases, air or vapours by liquid as separating agent
    • B01D47/06—Spray cleaning
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D47/00—Separating dispersed particles from gases, air or vapours by liquid as separating agent
    • B01D47/06—Spray cleaning
    • B01D47/063—Spray cleaning with two or more jets impinging against each other
    • 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
    • B01D53/74—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
    • B01D2259/00—Type of treatment
    • B01D2259/80—Employing electric, magnetic, electromagnetic or wave energy, or particle radiation
    • B01D2259/816—Sonic or ultrasonic vibration
    • 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

Definitions

  • the present invention relates to an improved, simultaneous removal method and apparatus for sulfur oxides and nitrogen oxides contained in exhaust gas, and more particularly, to an improved wet method, wherein sulfur oxides and nitrogen oxides contained in exhaust gas are simultaneously removed
  • the present invention relates to a method and device for simultaneous removal of sulfur oxides and nitrogen oxides contained in exhaust gas that can be removed.
  • Wet limestone desulfurization equipment is generally used to remove sulfur oxides (SO x ) from air pollution emission facilities using fossil fuels, but since the desulfurization rate is 80% to 90%, a part of the generated amount is discharged to the atmosphere.
  • SO x sulfur oxides
  • air pollution prevention facilities using fossil fuels are arranged in the order of selective catalytic reduction, electrostatic precipitators, and flue gas desulfurization (FGD).
  • FGD flue gas desulfurization
  • ammonia or urea is injected in a gaseous state to reduce nitrogen oxides to nitrogen (N 2 ) gas to remove them, and the flue gas desulfurization device injects limestone slurry to absorb sulfurous acid (SO 2 ) gas into the limestone slurry liquid It is oxidized and removed by converting it to solid gypsum (CaSO 4 ).
  • SO 2 sulfurous acid
  • CaSO 4 solid gypsum
  • Residual nitrogen oxides (NO x ) that are not removed even after treatment in the selective catalytic reduction method is mostly insoluble nitrogen monoxide (NO), so it is not removed even in the absorber of the flue gas desulfurization device and is unavoidably discharged to the atmosphere.
  • NO insoluble nitrogen monoxide
  • Patent Document 0001 a method of removing nitrogen oxides by plasma method and reacting them with Na 2 S, Na 2 SO 3 has been disclosed (Patent Document 0001, Non-Patent Document 0002), and an organic solvent such as alcohol or diol compound A method of adsorbing and removing SO x , NO x has also been disclosed (Patent Document 0002), but these prior arts require additional use of expensive Na 2 S, Na 2 SO 3 to simultaneously process desulfurization and denitrification, and polyols Desulfurization and denitrification solution, which is a complex solution containing system and/or polyglycol system, must be separately prepared and used, and the flue gas temperature must be adjusted before desulfurization and denitrification. there was.
  • Korean Patent No. 10-1724358 discloses a method for adsorption by making a hydrogen peroxide solution in an adsorption tower after oxidizing flue gas with ozone
  • Korean Patent No. 10-1724358 discloses iron-ethylenediaminetetraacetic acid ( Fe-EDTA) and a method for electrochemical removal by utilizing the reaction of NO has been disclosed, but these prior technologies have problems such as construction of a new process, and also Korean Patent Application No. 10-2019-0042045 (application date: 2019.04. .10.) describes the simultaneous removal method and device for sulfur oxides and nitrogen oxides contained in exhaust gas.
  • Fe-EDTA iron-ethylenediaminetetraacetic acid
  • Patent Document 0001 Republic of Korea Patent No. 10-1800517 (published on: 2017.07.11)
  • Patent Document 0002 Republic of Korea Patent No. 10-1871197 (published on: 2017.02.08)
  • Patent Document 0003 Republic of Korea Patent Registration No. 10-1724358 (published on March 9, 2017)
  • Patent Document 0004 Korean Patent Application 10-2019-0042045 (Application Date: 2019.04.10.)
  • Non-Patent Document 0001 Journal of Korean Society for Atmospheric Environment Vol. 31, No. 2, April 2015, pp. 143 ⁇ 156
  • Non-Patent Document 0002 Moo Been Chang, How Ming Lee, Feeling Wu & Chi Ren Lai, J. Air & Waste Manage. Assoc. , 54:941 ⁇ 949
  • the main object of the present invention is that it is possible to simultaneously perform a denitrification process and a desulfurization process of exhaust gas in one wet treatment process, and to change equipment for denitrification in the previously operated wet desulfurization process or input expensive additives for denitrification
  • An object of the present invention is to provide a method and apparatus for simultaneously removing sulfur oxides and nitrogen oxides contained in exhaust gas as a more improved method while being able to economically treat sulfur oxides and nitrogen oxides at the same time without it.
  • an embodiment of the present invention provides a method for simultaneously removing sulfur oxides and nitrogen oxides contained in exhaust gas, (a) reacting the exhaust gas with ozone to provide nitrogen contained in the exhaust gas oxidizing the oxide; (b) mixing an organic acid or an organic acid salt with an alkaline earth metal compound in an aqueous solution or slurry state to obtain an absorbent; and (c) contacting the exhaust gas oxidized by reaction with ozone in step (a) with the absorbent in step (b) to perform denitrification and desulfurization of the exhaust gas, wherein the step (c) provides a method for simultaneously removing sulfur oxides and nitrogen oxides contained in exhaust gas, characterized in that the absorbent with the exhaust gas is subjected to ultrasonic treatment.
  • the alkaline earth metal compound of step (b) may be selected from the group consisting of calcium carbonate, calcium hydroxide, and mixtures thereof.
  • dicarboxylic acid having 1 to 20 carbon atoms
  • mixtures thereof can be characterized as
  • the content of the organic acid or salt of the organic acid in step (b) may be 1 ppm to 3,000 ppm compared to the solid content in the absorbent.
  • the step (a) may include oxidizing nitrogen monoxide (NO) contained in the exhaust gas to nitrogen dioxide (NO 2 ) by reacting the exhaust gas with ozone. .
  • NO nitrogen monoxide
  • a desulfurization reaction is performed by a reaction between sulfur oxides in exhaust gas and an alkaline earth metal compound in the absorbent, and the denitrification in step (c) is the denitrification of exhaust gas.
  • Alkaline earth metal sulfite produced by the desulfurization reaction of sulfur oxide and an alkaline earth metal compound in which an organic acid or a salt of an organic acid is mixed in the absorbent, and nitrogen monoxide (NO) contained in the exhaust gas in step (a) are reacted with ozone
  • nitrogen dioxide (NO 2 ) is It may be characterized in that the denitrification reaction is converted into nitrogen (N 2 ).
  • Another embodiment of the present invention provides an apparatus for simultaneously removing sulfur oxides and nitrogen oxides contained in exhaust gas, comprising: a gas phase reaction unit for oxidizing nitrogen oxides contained in the exhaust gas by reacting the exhaust gas with ozone; an absorbent storage unit for storing an absorbent obtained by mixing an organic acid or a salt of an organic acid with an alkaline earth metal compound in an aqueous solution or slurry state; a wet reaction unit for performing denitrification and desulfurization of the exhaust gas containing sulfur oxides and nitrogen oxides by contacting the absorbent in the absorbent storage unit with the exhaust gas oxidized in the gas phase reaction unit; and an energy applying unit provided in the wet reaction unit and performing ultrasonic treatment on the absorbent in contact with the exhaust gas oxidized in the gas phase reaction unit; of the simultaneous removal device.
  • the wet reaction unit includes a lower storage unit for storing the absorbent sprayed by the following absorbent spray nozzle, an absorbent spray nozzle to which the absorbent is sprayed, and a circulation pipe for transferring the absorbent to the spray nozzle, , the absorbent may be sprayed from the lower storage unit through the circulation pipe by the spray nozzle, and then move back to the lower storage unit to be circulated.
  • the energy applying unit may be provided in at least one of a lower storage unit and a circulation pipe in the wet reaction unit to perform ultrasonic treatment, and in this case, the energy applying unit is circulated in the wet reaction unit. It may be provided only in the pipe to perform ultrasonic treatment, or it may be provided only in the lower storage unit in the wet reaction unit to perform ultrasonic treatment, or may be provided in the lower storage unit and the circulation pipe in the wet reaction unit to perform ultrasonic treatment, respectively.
  • the gas phase reaction unit may be characterized as a duct or a reactor for transferring the exhaust gas.
  • the alkaline earth metal compound in the absorbent storage unit may be selected from the group consisting of calcium carbonate, calcium hydroxide, and mixtures thereof.
  • the gas phase reaction unit may include a reaction of oxidizing nitrogen monoxide (NO) contained in the exhaust gas to nitrogen dioxide (NO 2 ) by reacting the exhaust gas with ozone.
  • NO nitrogen monoxide
  • the desulfurization in the wet reaction unit is a desulfurization reaction by reaction of sulfur oxides in the exhaust gas with an alkaline earth metal compound in the absorbent, and the denitrification in the wet reaction unit is the denitrification of the exhaust gas.
  • the gas phase reaction unit may include a grid type nozzle for injecting ozone in order to sufficiently mix the exhaust gas and ozone, and the nozzle may be installed before the wet reaction unit.
  • the wet reaction unit is an absorption tower used in a flue gas desulfurization device in a thermal power plant, and the absorbent supplied from the absorbent storage unit is sprayed in the absorption tower, whereby the sprayed absorbent and the gas phase are sprayed. It may be characterized in that the exhaust gas oxidized in the reaction unit is contacted to perform denitrification and desulfurization of the exhaust gas containing sulfur oxides and nitrogen oxides.
  • the present invention by performing the exhaust gas denitration process as a wet process under the same operating conditions as the desulfurization process, it is possible to simultaneously perform the exhaust gas denitration process and the desulfurization process in one wet process facility (wet flue gas desulfurization device). Rather, it is possible to perform both denitrification and desulfurization without changing facilities for denitrification in the wet desulfurization process that was previously operated, so it is economical and more efficient when different operating conditions are applied to each of the denitrification process and the desulfurization process. It has the effect of reducing efficiency and side effects.
  • nitrogen monoxide (NO) of exhaust gas with low reactivity with ozone is converted into nitrogen dioxide (NO 2 ) with high reactivity, and an absorbent is obtained through the input of organic acid or salt of organic acid, thereby reducing the exhaust gas
  • ultrasonic treatment is performed on the absorbent in contact with the exhaust gas, thereby increasing the reaction rate of sulfur oxides in the exhaust gas and the absorbent, and at the same time, denitrification of an intermediate product of the generated sulfur oxides It has the effect of realizing high exhaust gas denitrification and desulfurization efficiency without the addition of expensive denitrification additives (Na 2 S, Na 2 SO 3 ) by using zero.
  • FIG. 1 is a schematic diagram of an apparatus for simultaneously removing sulfur oxides and nitrogen oxides in exhaust gas according to an embodiment of the present invention.
  • FIG. 2 is a schematic diagram of an apparatus for simultaneously removing sulfur oxides and nitrogen oxides in exhaust gas according to another embodiment of the present invention.
  • FIG. 3 is a block diagram of a device for simultaneously removing sulfur oxides and nitrogen oxides applied to an embodiment of the present invention.
  • the present invention provides a method for simultaneously removing sulfur oxides and nitrogen oxides contained in exhaust gas, comprising the steps of: (a) oxidizing nitrogen oxides contained in the exhaust gas by reacting the exhaust gas with ozone; (b) mixing an organic acid or an organic acid salt with an alkaline earth metal compound in an aqueous solution or slurry state to obtain an absorbent; and (c) contacting the exhaust gas oxidized by reaction with ozone in step (a) with the absorbent in step (b) to perform denitrification and desulfurization of the exhaust gas, wherein the step (c) relates to a method for simultaneously removing sulfur oxides and nitrogen oxides contained in exhaust gas, characterized in that the absorbent with the exhaust gas is subjected to ultrasonic treatment.
  • the present invention also provides an apparatus for simultaneously removing sulfur oxides and nitrogen oxides contained in exhaust gas, comprising: a gas phase reaction unit for oxidizing nitrogen oxides contained in the exhaust gas by reacting the exhaust gas with ozone; an absorbent storage unit for storing an absorbent obtained by mixing an organic acid or a salt of an organic acid with an alkaline earth metal compound in an aqueous solution or slurry state; a wet reaction unit for performing denitrification and desulfurization of the exhaust gas containing sulfur oxides and nitrogen oxides by contacting the absorbent in the absorbent storage unit with the exhaust gas oxidized in the gas phase reaction unit; and an energy applying unit provided in the wet reaction unit and performing ultrasonic treatment on the absorbent in contact with the exhaust gas oxidized in the gas phase reaction unit; It relates to a simultaneous removal device of
  • the method and device for simultaneously removing sulfur oxides and nitrogen oxides contained in exhaust gas use a wet desulfurization process for removing sulfur oxides contained in exhaust gas as well as desulfurization of sulfur oxides and nitrogen oxides.
  • the present invention relates to a method and apparatus for performing this denitrification process, and it is possible to simultaneously perform a denitration process and a desulfurization process of exhaust gas with one wet treatment process. It is possible to economically treat sulfur oxides and nitrogen oxides simultaneously without adding additives for denitrification.
  • FIG. 1 is a schematic diagram of an apparatus for simultaneously removing sulfur oxides and nitrogen oxides in exhaust gas according to an embodiment of the present invention
  • FIG. 2 is an apparatus for simultaneously removing sulfur oxides and nitrogen oxides from exhaust gas according to another embodiment of the present invention.
  • FIG. 3 is a configuration diagram of a device for simultaneously removing sulfur oxides and nitrogen oxides applied to an embodiment of the present invention.
  • the device for simultaneously removing sulfur oxides (SO x ) and nitrogen oxides (NO x ) contained in exhaust gas according to the present invention includes a gas phase reaction unit 10 , an absorbent storage unit 20 , a wet reaction unit 30 , and energy application part 40 .
  • the gas phase reaction unit 10 is installed to be positioned between an exhaust gas generating source (not shown) and the wet reaction unit 30 .
  • the exhaust gas discharged from the exhaust gas generating source is supplied to the gas phase reaction unit 10 , and then is supplied to the wet reaction unit 30 through the gas phase reaction unit 10 .
  • the gas phase reaction unit 10 reacts the exhaust gas with ozone to oxidize nitrogen oxides (NO x ) contained in the exhaust gas [step (a)].
  • the nitrogen oxides (NO x ) contained in the exhaust gas are mostly composed of nitrogen monoxide (NO), which is difficult to wet-treat due to its low reactivity and solubility, and in the present invention, nitrogen monoxide (NO) in these nitrogen oxides is converted into ozone (O 3 )
  • NO 2 nitrogen dioxide
  • NO 2 nitrogen dioxide
  • nitrogen monoxide (NO) included in the exhaust gas may be converted into nitrogen dioxide (NO 2 ) according to the following Reaction Equation 1.
  • the exhaust gas and ozone may be injected into the gas phase reaction unit 10 by controlling the flow rate using a mass flow meter 11 or the like, and the gas phase reaction unit 10 is a duct 15 for transporting the exhaust gas.
  • a Teflon tube reactor 12 or the like may be used, but is not limited thereto.
  • the gas residence time in the reactor can be changed, the gas residence time in the gas phase reaction unit can change the gas residence time in the reactor, and the gas residence time in the gas phase reaction unit Since silver is proportional to the volume of the reactor, it may be typically 1 second to 30 seconds, preferably 2 seconds to 10 seconds, but is not limited thereto.
  • the gas phase reaction unit 10 includes a grid-type nozzle (not shown) for injecting ozone in order to sufficiently mix the exhaust gas and ozone, and the nozzle reacts wet as shown in FIG. 1 . It can be seen that it is installed in the previous stage.
  • the reaction in the gas phase reaction unit 10 reacts the exhaust gas and ozone under the conditions of 160 ° C. or less, preferably 130 ° C. or less, and the molar ratio of ozone to nitrogen oxide is equivalent to the reaction with nitrogen oxide. Therefore, ozone may be injected as much as the equivalent to remove nitrogen oxides, and if an excess of ozone is used, ozone may be emitted into the atmosphere and become contaminated. Preferably, the equivalent ratio of ozone to nitrogen oxides is 1 or less. Do.
  • the absorbent storage unit 20 stores an absorbent obtained by mixing an organic acid or a salt of an organic acid with an alkaline earth metal compound in an aqueous solution state or a slurry state, and stores the stored absorbent in the wet reaction unit 30 for denitrification and desulfurization. supply [step (b)].
  • the absorbent storage unit 20 may be connected to the wet reaction unit through a connection pipe 21 .
  • the connection pipe 21 has one side connected to the absorbent storage unit 20, and the other side connected to the wet reaction unit 30, and the absorbent stored in the absorbent storage unit 20 is connected to the wet reaction unit 30 through a connection pipe. can be supplied, and a pump, a valve, etc. for this may be additionally provided.
  • the absorbent may be prepared by mixing an organic acid or a salt of an organic acid with an alkaline earth metal compound in an aqueous solution or slurry state in which an alkaline earth metal compound is dispersed in water.
  • the mixing can be easily performed by applying a method used in the art.
  • the alkaline earth metal compound may be at least one selected from the group consisting of calcium carbonate and calcium hydroxide, and calcium carbonate is preferable in terms of processing cost and usefulness.
  • the salt of may preferably be an alkaline earth metal salt of formic acid.
  • the absorbent according to the present invention is prepared by mixing an alkaline earth metal compound with an organic acid or a salt of an organic acid, so that the surface of the alkaline earth metal compound is continuously consumed while performing an ion exchange reaction with the organic acid on the surface of the alkaline earth metal compound, so the particle size of the absorbent can be made smaller.
  • This principle is very similar to CMP in semiconductor processing, and the etching rate of the calcium carbonate surface depends on the acid content and the degree of movement of the particles. The higher the acid content or the greater the particle movement, the smaller the particle size.
  • alkaline earth metal compounds have a very low solubility in water, so there is a problem that reactivity with sulfur oxides and nitrogen oxides occurring in an aqueous phase is very low.
  • This problem can be solved by adding an organic acid, because the alkaline earth metal compound reacts with the organic acid to form an alkali salt such as a calcium salt having improved water solubility. That is, since sulfur oxide can only react with calcium in the aqueous phase, the higher the concentration of calcium salt soluble in water in the wet process, the greater the number of calcium ions in contact with the sulfur oxide, and the more efficiently the sulfur oxide is removed. can
  • formic acid has half carbon number than dibasic acid and has excellent water solubility and physicochemical properties.
  • the particle size of the absorbent can be drastically reduced and an alkali salt with improved solubility is produced.
  • formic acid which has half carbon number than dibasic acid (eg HOOC-CH 2 -CH 2 -COOH)
  • HCOOH formic acid
  • dibasic acid eg HOOC-CH 2 -CH 2 -COOH
  • the particle size of the absorbent is made smaller, thereby reducing the reactivity with sulfur oxides and nitrogen oxides in the exhaust gas. The absorption rate can be further improved.
  • the organic acid or salt of the organic acid contained in the absorbent may be 1 ppm to 3,000 ppm, preferably 10 ppm to 2,000 ppm, based on the solid content in the absorbent.
  • the organic acid or salt of the organic acid is mixed at less than 1 ppm relative to the solid content of the absorbent, the mixed effect of the organic acid or salt of the organic acid cannot be exhibited. may occur.
  • the organic acid-containing absorbent is acetic acid, propionic acid, butyl carboxylic acid, pentyl carboxylic acid, adipic acid, and succinic acid in addition to formic acid in order to accelerate the solubilization of calcium from the absorbent and further promote desulfurization and denitrification.
  • maleic acid, malic acid, etc. containing a carboxyl group or may further contain an organic acid containing a carboxyl group and a hydroxyl group at the same time, such as 3-hydroxy-propionic acid, hydroxy-acetic acid, etc.
  • the organic acid containing a carboxyl group and a hydroxyl group at the same time 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 stores the absorbent, and the absorbent may be stored in an aqueous solution state or a slurry state.
  • the storage tank 22 may be connected to the wet reaction unit 30 through a connection pipe 21 .
  • the stirring unit 23 is installed in the storage tank 22, and by stirring the absorbent stored in the storage tank 22 to make it uniform, the reaction between the organic acid or the salt of the organic acid and the alkaline earth metal compound can be promoted. there is.
  • the absorbent in the absorbent storage unit 20 and the exhaust gas oxidized in the gas phase reaction unit 10 are supplied to the wet reaction unit 30, and the exhaust gas supplied to the wet reaction unit 30 and the absorbent react in a wet manner. Denitrification and desulfurization of the exhaust gas are performed by contacting the unit [step (c)].
  • Desulfurization in the wet reaction unit 30 is performed by a reaction between sulfur oxides in exhaust gas and alkaline earth metal compounds in the absorbent, and denitrification is generated by a desulfurization reaction between sulfur oxides in exhaust gas and alkaline earth metal compounds in the absorbent. It is made by the reaction of alkaline earth metal sulfite (Sulfite, SO 3 ), which is an intermediate product, and nitrogen dioxide absorbed by oxidizing nitrogen monoxide in exhaust gas.
  • alkaline earth metal sulfite SO 3
  • sulfuric acid is added to the limestone slurry liquid sprayed in the process of passing sulfur oxides of exhaust gas into a liquid reactor or passing through an absorption tower of a flue gas desulfurization device in a thermal power plant, etc.
  • Desulfurization may occur as the cargo is absorbed.
  • calcium ions when an organic acid or a salt of an organic acid is added, calcium ions can be rapidly generated according to Schemes 4 and 5, and the calcium ions generated in this way are sulfite ions previously generated according to Scheme 6
  • Calcium sulfite (CaSO3) is produced by the reaction with the calcium sulfite, which reacts with nitrogen dioxide generated in the gas phase reaction unit previously to be changed into calcium sulfate, and the nitrogen dioxide is converted into nitrogen to perform denitrification reaction.
  • sulfur dioxide contained in the exhaust gas is finally converted to calcium sulfate (calcium salt) through sulfite ions (SO 3 2- ) to undergo a desulfurization reaction, thereby being removed from the exhaust gas.
  • calcium sulfite (CaSO 3 ) produced by the desulfurization of sulfur dioxide is used as a reducing agent for nitrogen oxides as shown in Scheme 7, and this reaction with nitrogen dioxide produces nitrogen (N 2 ) and calcium sulfate (CaSO 4 ) is created Therefore, the calcium sulfite, which can be produced by the desulfurization reaction, contains the organic acid in the calcium carbonate, so that the reaction can proceed more quickly, and in this case, the reaction can proceed more efficiently when the ultrasonic treatment is performed,
  • a method of using the calcium sulfite for denitrification corresponds to a technical feature of the present invention, and accordingly, nitrogen dioxide in the exhaust gas is converted to nitrogen (N 2 ) and removed from the exhaust gas.
  • the organic acid or salt of the organic acid mixed with the absorbent not only improves the absorption of sulfur oxides but also the absorption of nitrogen oxides, and at the same time catalyzes the slow reactions of Schemes 2 and 3 to speed up the reaction rate as shown in Schemes 4 to 5.
  • calcium sulfite (CaSO 3 ) can play a decisive role in producing a lot.
  • the concentration of calcium sulfite as a reducing agent must be increased, and for this, the desulfurization rate must be increased. Therefore, in the present invention, Na 2 S, Na 2 which is conventionally applied to exhaust gas denitration reaction.
  • the denitrification and desulfurization efficiency of exhaust gas can be maximized by using an absorbent mixed with an organic acid or a salt of an organic acid under energy application without the use of expensive denitrification additives such as SO 3 .
  • the energy applying unit according to the present invention is provided in the wet reaction unit 30, it is possible to perform ultrasonic treatment on the absorbent in contact with the exhaust gas oxidized in the gas phase reaction unit.
  • the energy applying unit 40 may be used without limitation as long as it is a device capable of applying ultrasonic waves to the wet reaction unit by being attached to, connected to, or coupled to the inside or outside of the wet reaction unit 30 .
  • the output (W) of the ultrasonic wave applied from the energy applying unit 40 must be applied proportionally according to the scale of the wet reaction unit, and its frequency is usually 2 kHz to 2,000 kHz, Preferably, it can be applied in the range of 10 kHz to 400, more preferably, 20 kHz to 40 kHz, but is not limited thereto.
  • the wet reaction unit 30 may include a wet reactor 31 and a stirring unit 32, and, as described above, passes through the absorption tower 35 of a flue gas desulfurization device in a thermal power plant, etc. In the process, sulfur oxides and nitrogen oxides are absorbed into the limestone slurry liquid sprayed so that desulfurization and denitrification can be performed simultaneously.
  • the wet reaction unit includes a lower storage unit for storing the absorbent sprayed by the following absorbent spray nozzle, an absorbent spray nozzle to which the absorbent is sprayed, and a circulation pipe for transferring the absorbent to the spray nozzle, and the absorbent is a lower storage unit After being sprayed by the injection nozzle through the circulation pipe, it can be configured to move back to the lower storage unit and circulate.
  • the energy applying unit is provided only in the circulation pipe in the wet reaction unit to perform ultrasonic treatment, or to the lower part in the wet reaction unit. It may be provided only in the storage unit to perform ultrasonic treatment, or may be simultaneously provided in the lower storage unit and the circulation pipe in the wet reaction unit to perform ultrasonic treatment, respectively.
  • FIG. 2 shows a specific example in which the desulfurization reaction and the denitrification reaction according to the present invention can be performed in a conventional flue gas desulfurization apparatus in a thermal power plant.
  • An exhaust gas transport duct for transporting exhaust gas is used as a device corresponding to the gas phase reaction unit, and ozone generated by the ozone generator in the duct and nitrogen oxides (NO x ) in the exhaust gas, particularly nitrogen monoxide (NO) It is converted into nitrogen dioxide (NO 2 ) by oxidation reaction, and the product [mixed gas including nitrogen dioxide (NO 2 )] according to the oxidation reaction of nitrogen oxide by ozone passes through the absorption tower 35 in the existing flue gas desulfurization device, In addition, the slurry liquid supplied from the absorbent storage unit 20 containing the limestone slurry liquid used for the existing desulfurization reaction is sprayed upward or downward in the absorption tower, and eventually the spray liquid falls downward according to gravity.
  • NO x nitrogen oxides
  • the sprayed slurry liquid reacts with the product [nitrogen dioxide (NO 2 ) containing mixed gas] according to the oxidation reaction of nitrogen oxides by the ozone, so that the desulfurization reaction and the denitration reaction are performed simultaneously.
  • NO 2 nitrogen dioxide
  • the wet reaction unit in the present invention corresponds to an absorption tower used in a flue gas desulfurization device in a thermal power plant, and the absorbent supplied from the absorbent storage unit according to the present invention is sprayed in the absorption tower, so that the sprayed absorbent and
  • the exhaust gas oxidized in the gas phase reaction unit according to the present invention is brought into contact to perform denitrification and desulfurization of the exhaust gas containing sulfur oxides and nitrogen oxides, and the energy applying unit is a circulation pipe in the wet reaction unit (absorption tower).
  • the desulfurization and denitration device to perform ultrasonic treatment and to further increase the efficiency of denitrification and desulfurization by applying ultrasonic waves to the absorbent in contact with the exhaust gas circulating in the wet reaction unit (absorption tower) can be configured.
  • the present invention uses the slurry spraying device and the exhaust gas transport duct in the absorption tower used in the prior art as it is, and additionally uses the exhaust gas transport duct as a gas phase reaction unit for oxidation reaction with ozone,
  • the desulfurization reaction in the existing absorption tower can be achieved by mixing an alkaline earth metal compound in an aqueous solution or slurry state with an organic acid or a salt of an organic acid in the absorbent storage unit and using it as an absorbent, and adding only a method of applying ultrasonic waves to the wet reaction unit.
  • the denitrification reaction is performed, and an excellent effect can be exhibited to further improve the efficiency of each of these reactions.
  • the wet reactor according to the present invention includes the wet reactor 31 and the stirring unit 32, not the absorption tower method in a thermal power plant according to the prior art, the absorbent and the exhaust gas can be introduced respectively.
  • each inlet (not shown); a reaction unit (not shown) in which denitrification and desulfurization of the absorbent and exhaust gas are performed; an outlet through which the products of denitrification and desulfurization are discharged (not shown);
  • An energy generating unit (not shown) for applying ultrasonic waves to the reaction unit may be formed, and the stirring unit 32 is installed in the wet reactor 31, and absorbs the absorbent and exhaust gas supplied to the wet reactor. It is possible to promote denitrification and desulfurization of exhaust gas by stirring.
  • the stirring unit 32 can be applied without limitation as long as it is a member capable of increasing the gas-liquid contact efficiency of the absorbent and the exhaust gas, and may be an agitator, a bubble generator, or the like.
  • the exhaust gas may be discharged to the outside through the connection duct 33 after nitrogen oxides and sulfur oxides are removed by a desulfurization and denitrification process in the wet reaction unit, and at this time, the alkali salt generated in the wet reaction unit is an aqueous solution It may remain in the wet reaction unit in a state or slurry state, and may be later discharged to a treatment facility (not shown) to obtain calcium sulfate (gypsum) or be recycled.
  • a treatment facility not shown
  • An improved, simultaneous removal method and apparatus for sulfur oxides and nitrogen oxides contained in exhaust gas converts low-reactive nitrogen monoxide into highly reactive nitrogen dioxide by reaction with ozone, and then reacts with ozone.
  • a denitration reaction with improved efficiency is induced through the ultrasonic treatment, through which organic acid Or by supplying an absorbent in an aqueous solution or slurry state containing a salt of an organic acid to perform the denitration process in parallel under the same conditions as the desulfurization process, the ratio that appears when different operating conditions are applied to each of the denitrification process and the desulfurization process Efficiency and side effects can be reduced, and by applying the existing wet desulfurization facility without the addition of expensive denitrification additives, it is possible to effectively remove residual nitrogen oxides that are not removed in the selective catalytic reduction device while improving the des
  • Denitrification and desulfurization of the exhaust gas containing nitrogen oxides and sulfur oxides were performed using the apparatus shown in FIG. 2 .
  • the exhaust gas and ozone stayed in the gas phase reaction unit for 6 seconds, and the exhaust gas and ozone were reacted at room temperature and pressure to oxidize.
  • the oxidized exhaust gas is supplied to the wet reaction unit 30 at a rate of 4.8 m 3 /hr, and reacted with an absorbent under ultrasonic (20 kHz) treatment to measure the removal rates of nitrogen oxides and sulfur oxides with a combustion gas meter (testo350). Table 2 shows.
  • the absorbent was prepared by adding the organic acid and content of Table 2 compared to the calcium carbonate slurry of 20% solids, and the prepared absorbent was supplied to the wet reaction unit (100 L) in 50 L. At this time, the absorbent was used to pass through 90% of the 325 mesh.
  • Example 3 20 2000 - - 77 98.5
  • Example 4 20 1000 formic acid 500 91 100
  • Example 5 20 1000 formic acid 1,000 95.5 100
  • Example 6 20 2000 formic acid 500 94 100
  • Example 7 20 2000 formic acid 1,000 98.5 100
  • Example 8 20 2000 acetic acid 1,000 91 100 Comparative Example 1 - - - - 56 97 Comparative Example 2 - - formic acid 0.01 56 97 Comparative Example 3 - - formic acid 500 86 100
  • Sulfur oxide contained in exhaust gas which can simultaneously perform exhaust gas denitration process and desulfurization process in one wet process facility by performing the exhaust gas denitration process as a wet process under the same operating conditions as the desulfurization process and to a more improved, simultaneous removal method and apparatus for nitrogen oxides, and has industrial applicability.

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Abstract

La présente invention concerne un procédé et un appareil pour éliminer simultanément l'oxyde de soufre et l'oxyde d'azote contenus dans un gaz d'échappement et, plus précisément, un procédé et un appareil encore améliorés pour éliminer simultanément l'oxyde de soufre et l'oxyde d'azote contenus dans un gaz d'échappement, un traitement de dénitrification du gaz d'échappement étant effectué par voie humide dans les mêmes conditions de fonctionnement que dans un traitement de désulfuration, le traitement de dénitrification et le traitement de désulfuration du gaz d'échappement pouvant être effectués simultanément dans une seule installation de traitement par voie humide.
PCT/KR2020/013878 2020-10-08 2020-10-12 Procédé et appareil améliorés pour l'élimination simultanée de l'oxyde de soufre et de l'oxyde d'azote contenus dans un gaz d'échappement WO2022075506A1 (fr)

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