WO2011145534A1 - Exhaust-gas treatment device and exhaust-gas treatment method - Google Patents

Exhaust-gas treatment device and exhaust-gas treatment method Download PDF

Info

Publication number
WO2011145534A1
WO2011145534A1 PCT/JP2011/061105 JP2011061105W WO2011145534A1 WO 2011145534 A1 WO2011145534 A1 WO 2011145534A1 JP 2011061105 W JP2011061105 W JP 2011061105W WO 2011145534 A1 WO2011145534 A1 WO 2011145534A1
Authority
WO
WIPO (PCT)
Prior art keywords
wall surface
exhaust gas
gas treatment
flue
water
Prior art date
Application number
PCT/JP2011/061105
Other languages
French (fr)
Japanese (ja)
Inventor
涼吉 ▲濱▼口
弘貢 長安
泰稔 上田
敏秀 野口
守男 加賀見
Original Assignee
三菱重工メカトロシステムズ株式会社
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by 三菱重工メカトロシステムズ株式会社 filed Critical 三菱重工メカトロシステムズ株式会社
Publication of WO2011145534A1 publication Critical patent/WO2011145534A1/en

Links

Images

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
    • B01D53/46—Removing components of defined structure
    • B01D53/48—Sulfur compounds
    • B01D53/50—Sulfur oxides
    • B01D53/501—Sulfur oxides by treating the gases with a solution or a suspension of an alkali or earth-alkali or ammonium compound
    • B01D53/504—Sulfur oxides by treating the gases with a solution or a suspension of an alkali or earth-alkali or ammonium compound characterised by a specific device
    • 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
    • B01D2251/00—Reactants
    • B01D2251/30—Alkali metal compounds
    • B01D2251/304—Alkali metal compounds of sodium
    • 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
    • B01D2251/402—Alkaline earth metal or magnesium compounds of magnesium
    • 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

Definitions

  • the present invention relates to an exhaust gas treatment apparatus and an exhaust gas treatment method for removing SO 3 in combustion exhaust gas.
  • Combustion exhaust gas containing sulfur oxides such as SO 2 and SO 3 is discharged from a combustion furnace that burns fuel containing 0.5 wt% or more of sulfur such as heavy fuel or coal fuel.
  • SO 3 is generated when a part of SO 2 is oxidized in a high temperature environment. Therefore, the abundance of SO 3 is about several percent with respect to SO 2 .
  • SO 3 causes clogging and corrosion of the air heater and corrosion of the flue, and when it is cooled and discharged from the chimney, it causes purple smoke (blueish smoke). It is desirable.
  • Patent Document 1 discloses a method for spraying desulfurization wastewater containing dissolved salt such as Na 2 SO 4 into combustion exhaust gas as a method for removing SO 3 easily and inexpensively.
  • Patent Document 2 discloses a method of spraying desulfurization waste water from a wet desulfurization apparatus by a lime gypsum method into combustion exhaust gas.
  • JP 2006-326575 A (Claims 1, 9, paragraphs [0009] and [0025])
  • JP 2008-246406 A (Claim 1, Claim 14, Paragraphs [0007], [0041], [0046])
  • An object of the present invention is to provide an exhaust gas treatment apparatus and an exhaust gas treatment method that enable stable operation over a long period of time.
  • a first aspect of the present invention is an exhaust gas treatment device for removing SO 3 contained in combustion exhaust gas, and an aqueous solution containing a dissolved salt in the flue upstream of the wet desulfurization device Spraying means for spraying, and wall surface cleaning water is supplied to the wall surface of the flue along the circumferential direction of the wall surface of the flue, and the wall surface over the entire surface of the flue to which the dissolved salt adheres
  • An exhaust gas treatment apparatus including a wall surface cleaning pipe for forming a liquid film of cleaning water.
  • a second aspect of the present invention is an exhaust gas treatment method for removing SO 3 contained in combustion exhaust gas, wherein an aqueous solution containing a dissolved salt is sprayed on the flue upstream of the wet desulfurization apparatus, and
  • this exhaust gas treatment method wall surface washing water is supplied to the wall surface of the flue, and a liquid film of the wall surface washing water is formed on the entire surface of the flue to which the dissolved salt adheres.
  • wall cleaning pipes are provided along the circumferential direction of the flue wall surface, and wall cleaning water is supplied from the wall cleaning pipe toward the flue wall surface.
  • the wall surface cleaning pipe supplies the wall surface cleaning water so that the liquid film of the wall surface cleaning water is formed on the entire surface of the region where the dried dissolved salt adheres.
  • the wall surface washing water is supplied more stably, the dissolved salt is washed away, and the dissolved salt is prevented from being deposited on the flue wall surface. For this reason, the reduction
  • the exhaust gas treatment apparatus of the present invention can be stably operated over a long period of time.
  • the wall surface washing water is preferably used as desulfurization waste water of the wet desulfurization apparatus.
  • a wet electrostatic precipitator is provided after the wet desulfurization apparatus, and the wall surface washing water is used as waste water of the wet electrostatic precipitator.
  • the operation cost can be reduced by reusing the waste water generated in the exhaust gas treatment apparatus for the wall surface washing water.
  • a spray means cleaning pipe for supplying spray means cleaning water for cleaning the spray means may be provided above the spray means.
  • the spray means cleaning pipe is provided on the upper part of the spray means, and the spray means is washed by supplying cleaning water, thereby preventing the dissolved salt from adhering.
  • the spray means washing water is desulfurization waste water of the wet desulfurization apparatus.
  • a wet electrostatic precipitator is provided after the wet desulfurization apparatus, and the spray means cleaning water is used as waste water of the wet electrostatic precipitator.
  • the operation cost can be reduced by reusing the waste water generated in the exhaust gas treatment apparatus for the washing water of the spray means.
  • a recovery unit that is provided along a circumferential direction of the wall surface below the wall surface cleaning pipe and collects the wall surface cleaning water, and the wall surface cleaning water recovered by the recovery unit is used as the wall surface cleaning pipe.
  • the structure provided with the circulation part made to circulate to is preferable. It is preferable that the wall surface washing water is collected and recirculated as the wall surface washing water.
  • the said structure WHEREIN It is preferable to provide the alkali supply part which supplies an alkali to the collect
  • SO 2 or SO 3 in the combustion exhaust gas passing through the flue is absorbed by the wall surface washing water, the pH of the wall surface washing water decreases.
  • an alkali supply unit that supplies alkali to the circulating wall surface washing water, it is possible to prevent damage to the flue.
  • the wall surface washing water is supplied so as to form a liquid film over the entire area where the dissolved salt is sprayed and adheres, so that the dissolved and dried solidified on the flue wall No salt deposits are formed. Moreover, since the spraying means is washed, the dissolved salt is prevented from adhering to the spraying means and solidifying. For this reason, it is prevented that the flow path area decreases during the exhaust gas treatment. Further, since the washing water always flows on the wall surface, it is possible to prevent flue corrosion and repeated application of thermal stress to the flue wall surface, thereby preventing the flue from being damaged. As a result, the exhaust gas treatment device can be stably operated over a long period of time.
  • FIG. 6 is a schematic view of another embodiment of a spraying means. It is the schematic of the exhaust gas processing apparatus which concerns on 2nd Embodiment.
  • FIG. 1 is a schematic view of an exhaust gas treatment apparatus according to the first embodiment.
  • the exhaust gas treatment apparatus 100 is provided in a flue downstream of a boiler (combustion furnace) 110.
  • the exhaust gas treatment device 100 includes a denitration device 111, an air heater 112, a dry electrostatic precipitator 113, a wet desulfurization device 114, a wet electrostatic precipitator 116, and a chimney 115.
  • the boiler 110 is, for example, a boiler that burns heavy oil or coal containing a relatively large amount of sulfur.
  • the denitration device 111 removes nitrogen oxides (NOx) contained in the combustion exhaust gas flowing from the boiler 110.
  • NOx nitrogen oxides
  • the air heater 112 exchanges heat between combustion exhaust gas and combustion air required by a pushing fan (not shown). Thereby, the combustion air is heated by the sensible heat of the combustion exhaust gas and supplied to the boiler 110.
  • the dry electrostatic precipitator 113 collects dust in the combustion exhaust gas by electrostatic force.
  • the wet desulfurization apparatus 114 may employ any of a caustic soda method, a water mug method, and a gypsum lime method.
  • the wet desulfurization apparatus 114 includes an absorbent spray 120 for spraying a solution containing an SO 2 absorbent, a packed bed 121 disposed below the absorbent spray 120, and a storage provided below the packed bed 121. Part 122.
  • the filling layer 121 is configured to be provided with a resin filler, for example.
  • the reservoir 122 stores an aqueous solution of the absorbent.
  • An absorbent of SO 2 is supplied from the absorbent supply means 123 to the storage unit 122.
  • the absorbent is NaOH for the caustic soda method, Mg (OH) 2 for the water mug method, and CaO (lime) for the gypsum lime method.
  • Air is supplied to the reservoir 122 from an air supply means (not shown).
  • An absorbent supply pump 124 is provided between the absorbent spray 120 and the reservoir 122.
  • the absorbent supply pump 124 pumps the aqueous solution containing the absorbent in the reservoir 122 into the absorbent spray 120.
  • the pumped aqueous solution containing the absorbent is sprayed from the absorbent spray 120 into the wet desulfurization apparatus 114.
  • the absorbent and SO 2 reacts, sulfites and sulfates are produced.
  • NaOH and SO 2 react to become Na 2 SO 3
  • Na 2 SO 4 is generated by reaction with oxygen. Therefore, the aqueous solution stored in the storage unit 122 includes Na 2 SO 3 and Na 2 SO 4 .
  • the aqueous solution stored in the storage unit 122 includes CaSO 4 and MgSO 4 .
  • a wet electrostatic precipitator 116 may be provided in the flue downstream of the wet desulfurizer 114.
  • the wet electrostatic precipitator 116 always sprays cleaning water on the collecting part, and removes dust and SO 3 that could not be collected by electrostatic force.
  • the wet electrostatic precipitator 116 is supplied with an alkaline solution such as a NaOH aqueous solution or a Mg (OH) 2 aqueous solution for neutralization.
  • This alkaline solution becomes an aqueous solution containing a dissolved salt such as Na 2 SO 4 or MgSO 4 as a drainage solution after neutralization.
  • Spray means 140 is provided in the flue 130 between the dry electrostatic precipitator 113 and the wet desulfurizer 114.
  • FIG. 2A is an enlarged schematic view of the cross section of the flue 130.
  • the spraying means 140 is configured such that the nozzle 142 is attached to the dissolved salt spray pipe 141.
  • the dissolved salt spray pipe 141 extends in the depth direction of FIG. 2A.
  • a plurality of nozzles are attached to the dissolved salt spray pipe 141 in the depth direction of the paper surface of FIG. 2A.
  • the nozzle 142 is preferably a two-fluid nozzle that atomizes the liquid with pressurized air.
  • the combustion exhaust gas circulates between the dissolved salt spray pipes 141.
  • the absorbent supply pump 124 supplies the solution in the storage unit 122 to the spray means 140.
  • an extraction pump different from the absorbent supply pump 124 is provided in the storage unit 122, and the extraction pump supplies a solution (desulfurization drainage) containing the reaction product in the storage unit 122 to the spraying unit 140. good.
  • the flow path for supplying desulfurization effluent to the spray means 140 from the reservoir 122 dissolved supplies powder, such as Na 2 SO 4, MgSO 4 in the desulfurization effluent
  • a salt concentration adjusting means may be provided.
  • the solution supplied to the spraying means 140 includes a reaction product in a wet desulfurization apparatus and a dissolved salt derived from an absorbent (such as NaOH).
  • the spraying means 140 sprays the solution into the flue 130 as droplets having a diameter of 10 to 100 ⁇ m, preferably 20 to 50 ⁇ m, more preferably 25 to 35 ⁇ m.
  • Hot flue gas flows through the flue 130.
  • SO 3 contained in the combustion exhaust gas is adsorbed and fixed to the dissolved salt particles, and SO 3 is removed from the combustion exhaust gas.
  • a part of the sulfate contained in the dried dissolved salt particles reacts with SO 3 .
  • the reaction of the formula (1) proceeds with a part of Na 2 SO 4 and SO 3 .
  • the environment in which the solution is sprayed is set to be equal to or higher than the evaporation temperature of water because the water needs to evaporate while the sprayed droplets are scattered. Furthermore, to react with SO 3, it is more dew point of SO 3. Specifically, the temperature is 130 ° C. or higher, preferably 140 ° C. or higher.
  • FIG. 3A and 3B show another form of spraying means.
  • FIG. 3A is a cross-sectional view of the spraying means 140, and the spraying means cleaning unit 150 is installed on the upper part of the dissolved salt spray pipe 141.
  • the spraying means cleaning unit 150 includes a spraying means cleaning pipe 151 and a discharge hole 152. The washing water is discharged from the discharge hole 152 toward the dissolved salt spray pipe 141 of the spray means 140.
  • the spraying means cleaning pipe 151 is arranged in parallel to the dissolved salt spraying pipe 141, and a plurality of discharge holes 152 are provided in the extending direction of the spraying means cleaning pipe 151.
  • Wash water is discharged from the discharge hole 152.
  • the discharged wash water flows along the outer wall of the dissolved salt spray pipe 141. This prevents the dried dissolved salt from adhering to the outer wall of the spraying means cleaning pipe 151. As a result, it is possible to prevent the dissolved salt from adhering and depositing between the dissolved salt spray pipes 141 and reducing the flow area of the combustion exhaust gas.
  • the discharge of the washing water from the discharge hole 152 may be performed intermittently or continuously.
  • the cleaning water supplied to the spraying means cleaning pipe 151 is either industrial water, desulfurization effluent of the wet desulfurization apparatus 114 and neutralization effluent of the wet electrostatic precipitator 116, or a mixture of two or more of these. It is made with water. By using desulfurization effluent and neutralization effluent as the washing water, the operating cost of the exhaust gas treatment device can be reduced.
  • the wall surface cleaning pipe 160 is provided along the circumferential direction of the flue 130 between the wet desulfurization apparatus 114 and the dry electrostatic precipitator 113. As shown in FIG. 2A, the wall cleaning pipe 160 is provided with a plurality of holes 161 in the circumferential direction of the flue.
  • Wall cleaning water is continuously supplied from the hole 161 of the wall cleaning pipe 160 toward the wall 131 of the flue 130. Thereby, the liquid film of the wall surface cleaning water is formed on the wall surface 131 without lowering the temperature of the surrounding exhaust gas.
  • the installation position and the number of the wall surface cleaning pipes 160 are set so that a liquid film is formed over the entire surface of the flue where the dissolved salt particles adhere.
  • two or one wall cleaning pipe 160 is installed on the wall surface 131 on the downstream side of the spraying means 140.
  • the number of holes 161 provided in the wall surface cleaning pipe 160, the interval and the angle with respect to the wall surface, and the size of the holes 161 are such that a liquid film is formed over the entire area where the dissolved salt particles adhere. Set as appropriate.
  • the flue 130 is configured by welding an external reinforcing material such as C-shaped steel or L-shaped steel to the outside of the flue of the duct plate.
  • an external reinforcing material such as C-shaped steel or L-shaped steel
  • the flue 130 is configured by welding an external reinforcing material such as C-shaped steel or L-shaped steel to the outside of the flue of the duct plate.
  • the wall surface washing water is either industrial water, desulfurization effluent of the wet desulfurization device 114, or neutralization effluent of the wet electrostatic precipitator 116, or water in which two or more of these are mixed. By doing so, the operating cost of the exhaust gas treatment apparatus can be reduced.
  • the wall surface cleaning water flows along the wall surface of the flue 130 and flows into the wet desulfurization apparatus 114.
  • FIG. 4 is a schematic view of an exhaust gas treatment apparatus according to the second embodiment.
  • the exhaust gas treatment apparatus 200 is provided with a collection unit and a circulation unit for collecting and circulating the wall surface cleaning water, and other configurations are the same as those of the first embodiment.
  • the wet desulfurization apparatus 214 adopts a gypsum lime method.
  • the spray means 240 and the wall surface cleaning pipe 260 are installed in the flue 230 between the wet desulfurization apparatus 214 and the dry electrostatic precipitator 213 as in the first embodiment.
  • the recovery unit 280 is installed along the circumferential direction of the flue 230, similarly to the wall surface cleaning pipe 260.
  • the collection unit 280 is, for example, a bowl-shaped flow path.
  • the collection unit 280 is connected to the circulation unit 290.
  • the circulation unit 290 is installed outside the flue 230 and includes a wall surface cleaning water tank 291 and a wall surface cleaning water supply pump 292.
  • Wall surface cleaning water is continuously supplied from the wall surface cleaning pipe 260 toward the wall surface of the flue 230, and the wall surface cleaning water flows down while forming a liquid film on the wall surface of the flue 230.
  • the wall surface washing water that has flowed down is collected by the collection unit 280.
  • the collected wall surface washing water is transferred to the wall surface washing water tank 291 and stored.
  • the wall surface cleaning water in the wall surface cleaning water tank 291 is pumped up by the wall surface cleaning water supply pump 292 and circulated through the wall surface cleaning pipe 260.
  • a cleaning water supply unit 293 and a pH adjuster supply unit 294 are connected to the wall surface cleaning water tank 291.
  • the wall surface washing water tank 291 is provided with a stirring device 295.
  • the cleaning water supply unit 293 supplies the wall surface cleaning water to the wall surface cleaning water tank.
  • the wall surface cleaning water to be replenished is industrial water, neutralized waste water from the wet electrostatic precipitator 216, or a mixed solution thereof.
  • the pH adjusting agent supply unit 294 supplies the pH adjusting agent to the wall surface cleaning water tank 291.
  • the pH of the wall surface cleaning water is adjusted to a neutral level.
  • the pH adjuster is an aqueous solution such as NaOH, Mg (OH) 2 , or CaO.
  • a recovery unit cleaning unit 281 may be installed below the recovery unit 280.
  • the collection unit cleaning unit 281 is, for example, a spray.
  • a part of the wall surface cleaning water pumped up by the wall surface cleaning water supply pump 292 is supplied to the recovery unit cleaning means 281.
  • the recovery unit cleaning means 281 intermittently injects cleaning water onto the outer wall of the recovery unit 280. Thereby, it can prevent that dissolved salt adheres to the outer wall of the collection
  • the sprayed cleaning water flows into the wet desulfurization device 214.

Landscapes

  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Environmental & Geological Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Biomedical Technology (AREA)
  • Analytical Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Treating Waste Gases (AREA)
  • Gas Separation By Absorption (AREA)

Abstract

Disclosed are an exhaust-gas treatment device and an exhaust-gas treatment method that allow stable operation over long periods of time. The disclosed exhaust-gas treatment device (100), which removes SO3 from a combustion exhaust gas, is provided with: a spray means (140) which sprays an aqueous solution containing a dissolved salt into a flue (130) upstream of a wet desulfurization device (114); and wall-cleaning piping (160), along the walls of the flue (130) in the circumferential direction thereof, which supplies wall-cleaning water to the walls of the flue, thereby forming a liquid film of said wall-cleaning water across the entire surface of the region of the flue (130) to which the aforementioned dissolved salt becomes attached. In the disclosed exhaust-gas treatment method, which removes SO3 from a combustion exhaust gas, an aqueous solution containing a dissolved salt is sprayed into a flue (130) upstream of a wet desulfurization device (114), and wall-cleaning water is supplied to the walls of the flue (130), thereby forming a liquid film of said wall-cleaning water across the entire surface of the region of the flue (130) to which the aforementioned dissolved salt becomes attached.

Description

排ガス処理装置及び排ガス処理方法Exhaust gas treatment apparatus and exhaust gas treatment method
　本発明は、燃焼排ガス中のＳＯ３を除去する排ガス処理装置及び排ガス処理方法に関する。 The present invention relates to an exhaust gas treatment apparatus and an exhaust gas treatment method for removing SO 3 in combustion exhaust gas.
　重質燃料や石炭燃料といった硫黄分を０．５ｗｔ％以上含む燃料を燃焼させる燃焼炉からは、ＳＯ２、ＳＯ３といった硫黄酸化物を含む燃焼排ガスが排出される。
　ＳＯ３は、ＳＯ２の一部が高温環境下で酸化されて発生する。したがって、ＳＯ３の存在量はＳＯ２に対して数％程度である。しかしながら、ＳＯ３は、エアヒータの詰まりや腐食、煙道の腐食の原因となり、かつ、煙突から冷却され排出されると紫煙（blueish smoke）の原因となることから、排出濃度を数ｐｐｍ以下に抑えることが望ましい。 Combustion exhaust gas containing sulfur oxides such as SO 2 and SO 3 is discharged from a combustion furnace that burns fuel containing 0.5 wt% or more of sulfur such as heavy fuel or coal fuel.
SO 3 is generated when a part of SO 2 is oxidized in a high temperature environment. Therefore, the abundance of SO 3 is about several percent with respect to SO 2 . However, SO 3 causes clogging and corrosion of the air heater and corrosion of the flue, and when it is cooled and discharged from the chimney, it causes purple smoke (blueish smoke). It is desirable.
　ＳＯ３を除去する方法として、アンモニアガスを燃焼排ガス中に吹き込むアンモニア注入法が知られている。また、特許文献１に、安価で簡便にＳＯ３を除去する方法として、Ｎａ２ＳＯ４等の溶解塩を含む脱硫排水を燃焼排ガス中に噴霧する方法が開示されている。特許文献２に、石灰石膏法による湿式脱硫装置からの脱硫排水を燃焼排ガス中に噴霧する方法が開示されている。 As a method for removing SO 3 , an ammonia injection method in which ammonia gas is blown into combustion exhaust gas is known. Patent Document 1 discloses a method for spraying desulfurization wastewater containing dissolved salt such as Na 2 SO 4 into combustion exhaust gas as a method for removing SO 3 easily and inexpensively. Patent Document 2 discloses a method of spraying desulfurization waste water from a wet desulfurization apparatus by a lime gypsum method into combustion exhaust gas.
特開２００６－３２６５７５号公報（請求項１、請求項９、段落［０００９］、［００２５］）JP 2006-326575 A (Claims 1, 9, paragraphs [0009] and [0025]) 特開２００８－２４６４０６号公報（請求項１、請求項１４、段落［０００７］、［００４１］、［００４６］）JP 2008-246406 A (Claim 1, Claim 14, Paragraphs [0007], [0041], [0046])
　特許文献１及び特許文献２に開示される排ガス処理装置では、１５０℃～２００℃程度の高温ガス雰囲気中に溶解塩を含む脱硫排水を噴霧するため、煙道の壁面に乾燥固化した溶解塩が付着し、成長する。また、乾燥固化した溶解塩の一部の巻き上がりにより、噴霧手段に溶解塩が付着して成長する。これらの付着物により、煙道の流路面積が減少し、煙道差圧が上昇することが問題となっている。更には、煙道の閉塞に繋がることが懸念される。 In the exhaust gas treatment apparatus disclosed in Patent Document 1 and Patent Document 2, since desulfurization waste water containing dissolved salt is sprayed in a high-temperature gas atmosphere of about 150 ° C. to 200 ° C., the dried and solidified dissolved salt is formed on the wall of the flue. Adhere and grow. Moreover, the dissolved salt adheres to the spraying means and grows due to a part of the dried and solidified dissolved salt being rolled up. These deposits are problematic in that the flow path area of the flue is reduced and the flue pressure differential is increased. Furthermore, there is a concern that this may lead to blockage of the flue.
　本発明は、長期間に亘り安定運転が可能となる排ガス処理装置及び排ガス処理方法を提供することを目的とする。 An object of the present invention is to provide an exhaust gas treatment apparatus and an exhaust gas treatment method that enable stable operation over a long period of time.
　上記課題を解決するために、本発明の第１の態様は、燃焼排ガス中に含まれるＳＯ３を除去する排ガス処理装置であって、湿式脱硫装置の上流側の煙道に溶解塩を含む水溶液を噴霧する噴霧手段と、前記煙道の壁面の周方向に沿って、前記煙道の壁面に対して壁面洗浄水を供給し、前記煙道の前記溶解塩が付着する領域の全面に前記壁面洗浄水の液膜を形成するための壁面洗浄配管とを備える排ガス処理装置である。 In order to solve the above problems, a first aspect of the present invention is an exhaust gas treatment device for removing SO 3 contained in combustion exhaust gas, and an aqueous solution containing a dissolved salt in the flue upstream of the wet desulfurization device Spraying means for spraying, and wall surface cleaning water is supplied to the wall surface of the flue along the circumferential direction of the wall surface of the flue, and the wall surface over the entire surface of the flue to which the dissolved salt adheres An exhaust gas treatment apparatus including a wall surface cleaning pipe for forming a liquid film of cleaning water.
　また本発明の第２の態様は、燃焼排ガス中に含まれるＳＯ３を除去する排ガス処理方法であって、湿式脱硫装置の上流側の煙道に、溶解塩を含む水溶液を噴霧するとともに、前記煙道の壁面に対して壁面洗浄水が供給され、前記煙道の前記溶解塩が付着する領域の全面に、前記壁面洗浄水の液膜が形成される排ガス処理方法である。 A second aspect of the present invention is an exhaust gas treatment method for removing SO 3 contained in combustion exhaust gas, wherein an aqueous solution containing a dissolved salt is sprayed on the flue upstream of the wet desulfurization apparatus, and In this exhaust gas treatment method, wall surface washing water is supplied to the wall surface of the flue, and a liquid film of the wall surface washing water is formed on the entire surface of the flue to which the dissolved salt adheres.
　本発明では、煙道壁面の周方向に沿って壁面洗浄配管を設け、壁面洗浄配管から煙道壁面に向かって壁面洗浄水を供給する構成とする。このとき、壁面洗浄配管は、乾燥した溶解塩が付着する領域の全面に壁面洗浄水の液膜が形成されるように、壁面洗浄水を供給する。こうすることで、壁面洗浄水をより安定的に供給して溶解塩を洗い流し、煙道壁面に溶解塩が堆積するのが防止される。このため、煙道の流通面積の減少を防止することができる。また壁面に常時洗浄水を流すために、煙道壁面に腐食が発生することが抑制されるとともに、煙道壁面に熱応力が繰り返し発生することが抑制され、煙道の損傷を防止することができる。その結果、本発明の排ガス処理装置は、長期に亘り安定した運転が可能となる。 In the present invention, wall cleaning pipes are provided along the circumferential direction of the flue wall surface, and wall cleaning water is supplied from the wall cleaning pipe toward the flue wall surface. At this time, the wall surface cleaning pipe supplies the wall surface cleaning water so that the liquid film of the wall surface cleaning water is formed on the entire surface of the region where the dried dissolved salt adheres. By doing so, the wall surface washing water is supplied more stably, the dissolved salt is washed away, and the dissolved salt is prevented from being deposited on the flue wall surface. For this reason, the reduction | decrease of the distribution area of a flue can be prevented. In addition, since flushing water always flows on the wall surface, the occurrence of corrosion on the flue wall surface is suppressed, and the repeated occurrence of thermal stress on the flue wall surface is suppressed, thereby preventing the flue from being damaged. it can. As a result, the exhaust gas treatment apparatus of the present invention can be stably operated over a long period of time.
　前記第１の態様において、前記壁面洗浄水が、前記湿式脱硫装置の脱硫排水とされることが好ましい。あるいは、前記湿式脱硫装置の後段に湿式電気集塵装置が設けられ、前記壁面洗浄水が、前記湿式電気集塵装置の排水とされることが好ましい。 In the first aspect, the wall surface washing water is preferably used as desulfurization waste water of the wet desulfurization apparatus. Alternatively, it is preferable that a wet electrostatic precipitator is provided after the wet desulfurization apparatus, and the wall surface washing water is used as waste water of the wet electrostatic precipitator.
　このように、排ガス処理装置内で生成する排水を壁面洗浄水に再利用することによって、運転コストを低減することができる。 Thus, the operation cost can be reduced by reusing the waste water generated in the exhaust gas treatment apparatus for the wall surface washing water.
　前記第１の態様において、前記噴霧手段の上部に、前記噴霧手段を洗浄する噴霧手段洗浄水を供給する噴霧手段洗浄配管が設けられる構成であっても良い。 In the first aspect, a spray means cleaning pipe for supplying spray means cleaning water for cleaning the spray means may be provided above the spray means.
　噴霧手段から溶解塩を含む水溶液が噴霧されると、乾燥固化した溶解塩の一部の巻き上がりにより、噴霧手段に溶解塩が付着する。このため、噴霧手段の間の煙道において、溶解塩の堆積により燃焼排ガスの流通面積の減少や閉塞といった問題が発生しやすい。前記構成のように、噴霧手段の上部に噴霧手段洗浄配管を設けて、洗浄水を供給して噴霧手段を洗浄することによって、溶解塩の付着を防止することができる。 When an aqueous solution containing a dissolved salt is sprayed from the spraying means, the dissolved salt adheres to the spraying means due to a part of the dried and solidified dissolved salt rolling up. For this reason, in the flue between the spraying means, problems such as reduction or blockage of the distribution area of the combustion exhaust gas are likely to occur due to the accumulation of dissolved salt. As in the above-described configuration, the spray means cleaning pipe is provided on the upper part of the spray means, and the spray means is washed by supplying cleaning water, thereby preventing the dissolved salt from adhering.
　前記構成において、前記噴霧手段洗浄水が、前記湿式脱硫装置の脱硫排水とされることが好ましい。あるいは、前記湿式脱硫装置の後段に湿式電気集塵装置が設けられ、前記噴霧手段洗浄水が、前記湿式電気集塵装置の排水とされることが好ましい。 In the above configuration, it is preferable that the spray means washing water is desulfurization waste water of the wet desulfurization apparatus. Alternatively, it is preferable that a wet electrostatic precipitator is provided after the wet desulfurization apparatus, and the spray means cleaning water is used as waste water of the wet electrostatic precipitator.
　このように、排ガス処理装置内で生成する排水を噴霧手段の洗浄水に再利用することによって、運転コストを低減することができる。 Thus, the operation cost can be reduced by reusing the waste water generated in the exhaust gas treatment apparatus for the washing water of the spray means.
　上記発明において、前記壁面洗浄配管の下方の前記壁面の周方向に沿って設けられ、前記壁面洗浄水を回収する回収部と、該回収部で回収された前記壁面洗浄水を、前記壁面洗浄配管に循環させる循環部とを備える構成が好ましい。
　前記壁面洗浄水を回収し、前記壁面洗浄水として再循環させることが好ましい。 In the above invention, a recovery unit that is provided along a circumferential direction of the wall surface below the wall surface cleaning pipe and collects the wall surface cleaning water, and the wall surface cleaning water recovered by the recovery unit is used as the wall surface cleaning pipe. The structure provided with the circulation part made to circulate to is preferable.
It is preferable that the wall surface washing water is collected and recirculated as the wall surface washing water.
　壁面洗浄水を回収し循環させることにより、壁面洗浄水が脱硫装置に流入することを防止することができる。このため、湿式脱硫装置の循環液の塩濃度低下を防止して、ＳＯ２，ＳＯ３の除去能力低下を防止することができる。 By collecting and circulating the wall surface washing water, it is possible to prevent the wall surface washing water from flowing into the desulfurization apparatus. For this reason, the fall of the salt concentration of the circulating liquid of a wet desulfurization apparatus can be prevented, and the fall of SO 2 and SO 3 removal ability can be prevented.
　前記構成において、前記回収された壁面洗浄水に、アルカリを供給するアルカリ供給部を備えることが好ましい。
　煙道を通過する燃焼排ガス中のＳＯ２やＳＯ３が壁面洗浄水に吸収されると、壁面洗浄水のｐＨが低下する。このように、循環される壁面洗浄水にアルカリを供給するアルカリ供給部を備えることにより、煙道の損傷を防止することができる。 The said structure WHEREIN: It is preferable to provide the alkali supply part which supplies an alkali to the collect | recovered wall surface washing water.
When SO 2 or SO 3 in the combustion exhaust gas passing through the flue is absorbed by the wall surface washing water, the pH of the wall surface washing water decreases. Thus, by providing an alkali supply unit that supplies alkali to the circulating wall surface washing water, it is possible to prevent damage to the flue.
　ＳＯ３を含む燃焼排ガスが流通する煙道壁面において、溶解塩が噴霧されて付着する領域の全面に液膜を形成するように壁面洗浄水が供給されるため、煙道壁面に乾燥固化した溶解塩の付着物が形成されない。また、噴霧手段が洗浄されるため、噴霧手段にも溶解塩が付着・固化することが防止される。このため、排ガス処理中に流路面積が減少することが防止される。さらに、壁面を常時洗浄水が流れるので、煙道の腐食や煙道壁面に熱応力が繰り返し加わることが防止され、煙道の損傷が防止される。この結果、排ガス処理装置を長期間に亘り安定運転させることが可能となる。 On the flue wall where combustion exhaust gas containing SO 3 circulates, the wall surface washing water is supplied so as to form a liquid film over the entire area where the dissolved salt is sprayed and adheres, so that the dissolved and dried solidified on the flue wall No salt deposits are formed. Moreover, since the spraying means is washed, the dissolved salt is prevented from adhering to the spraying means and solidifying. For this reason, it is prevented that the flow path area decreases during the exhaust gas treatment. Further, since the washing water always flows on the wall surface, it is possible to prevent flue corrosion and repeated application of thermal stress to the flue wall surface, thereby preventing the flue from being damaged. As a result, the exhaust gas treatment device can be stably operated over a long period of time.
第１実施形態に係る排ガス処理装置の概略図である。It is the schematic of the exhaust gas processing apparatus which concerns on 1st Embodiment. 乾式電気集塵装置と湿式脱硫装置との間の煙道の断面を拡大した概略図である。It is the schematic which expanded the cross section of the flue between a dry-type electrostatic precipitator and a wet desulfurization apparatus. 噴霧手段の概略図である。It is the schematic of a spraying means. 噴霧手段の別の実施形態の断面図である。It is sectional drawing of another embodiment of a spraying means. 噴霧手段の別の実施形態の概略図である。FIG. 6 is a schematic view of another embodiment of a spraying means. 第２実施形態に係る排ガス処理装置の概略図である。It is the schematic of the exhaust gas processing apparatus which concerns on 2nd Embodiment.
＜第１実施形態＞
　図１は、第１実施形態に係る排ガス処理装置の概略図である。排ガス処理装置１００はボイラ（燃焼炉）１１０の下流側の煙道に設けられる。排ガス処理装置１００は、脱硝装置１１１と、エアヒータ１１２と、乾式電気集塵装置１１３と、湿式脱硫装置１１４と、湿式電気集塵装置１１６と、煙突１１５とを備える。
　ボイラ１１０は、例えば、硫黄分を比較的多く含有する重油や石炭を燃焼させるボイラとされる。
　脱硝装置１１１は、ボイラ１１０から流入する燃焼排ガスに含まれる窒素酸化物（ＮＯｘ）を除去する。
　エアヒータ１１２は、燃焼排ガスと押し込みファン（不図示）によって要求される燃焼用空気とを熱交換させるものである。これにより、燃焼用空気は燃焼排ガスの顕熱によって加熱され、ボイラ１１０へと供給される。
　乾式電気集塵装置１１３は、燃焼排ガス中の煤塵を静電気力によって捕集するものである。 <First Embodiment>
FIG. 1 is a schematic view of an exhaust gas treatment apparatus according to the first embodiment. The exhaust gas treatment apparatus 100 is provided in a flue downstream of a boiler (combustion furnace) 110. The exhaust gas treatment device 100 includes a denitration device 111, an air heater 112, a dry electrostatic precipitator 113, a wet desulfurization device 114, a wet electrostatic precipitator 116, and a chimney 115.
The boiler 110 is, for example, a boiler that burns heavy oil or coal containing a relatively large amount of sulfur.
The denitration device 111 removes nitrogen oxides (NOx) contained in the combustion exhaust gas flowing from the boiler 110.
The air heater 112 exchanges heat between combustion exhaust gas and combustion air required by a pushing fan (not shown). Thereby, the combustion air is heated by the sensible heat of the combustion exhaust gas and supplied to the boiler 110.
The dry electrostatic precipitator 113 collects dust in the combustion exhaust gas by electrostatic force.
　本実施形態において、湿式脱硫装置１１４は、苛性ソーダ法、水マグ法、石膏石灰法のいずれかを採用したものであっても良い。湿式脱硫装置１１４は、ＳＯ２の吸収剤を含む溶液を噴霧する吸収剤噴霧スプレー１２０と、吸収剤噴霧スプレー１２０の下方に配置された充填層１２１と、充填層１２１の下方に設けられた貯留部１２２とを備える。
　充填層１２１は、例えば樹脂製の充填材が設けられた構成とされる。
　貯留部１２２には、吸収剤の水溶液が収納される。吸収剤供給手段１２３からＳＯ２の吸収剤が貯留部１２２に供給される。吸収剤は、苛性ソーダ法の場合ＮａＯＨ、水マグ法の場合Ｍｇ（ＯＨ）２、石膏石灰法の場合ＣａＯ（石灰）とされる。また、貯留部１２２には、空気供給手段（不図示）から空気が供給される。 In this embodiment, the wet desulfurization apparatus 114 may employ any of a caustic soda method, a water mug method, and a gypsum lime method. The wet desulfurization apparatus 114 includes an absorbent spray 120 for spraying a solution containing an SO 2 absorbent, a packed bed 121 disposed below the absorbent spray 120, and a storage provided below the packed bed 121. Part 122.
The filling layer 121 is configured to be provided with a resin filler, for example.
The reservoir 122 stores an aqueous solution of the absorbent. An absorbent of SO 2 is supplied from the absorbent supply means 123 to the storage unit 122. The absorbent is NaOH for the caustic soda method, Mg (OH) 2 for the water mug method, and CaO (lime) for the gypsum lime method. Air is supplied to the reservoir 122 from an air supply means (not shown).
　吸収剤噴霧スプレー１２０と貯留部１２２との間には、吸収剤供給ポンプ１２４が設けられている。吸収剤供給ポンプ１２４により、貯留部１２２内の吸収剤を含む水溶液が吸収剤噴霧スプレー１２０に汲み上げられる。汲み上げられた吸収剤を含む水溶液は、吸収剤噴霧スプレー１２０から湿式脱硫装置１１４内に噴霧される。これにより、吸収剤とＳＯ２とが反応し、亜硫酸塩及び硫酸塩が生成する。
　例えば苛性ソーダ法の場合、ＮａＯＨとＳＯ２とが反応してＮａ２ＳＯ３となり、酸素との反応によりＮａ２ＳＯ４が生成する。従って、貯留部１２２内に貯蔵される水溶液には、Ｎａ２ＳＯ３及びＮａ２ＳＯ４が含まれる。
　石灰石膏法の場合、ＣａＳＯ４・２Ｈ２Ｏ（石膏）が生成する。反応生成物を含む溶液は貯留部１２２に貯留される。従って、反応生成物は湿式脱硫装置１１４内で循環する。なお、貯留部１２２には、例えばＣａＳＯ３も溶解しているが、空気供給手段により供給される空気により積極的に酸化される。ＣａＳＯ４は水に対して難溶性であるため、大部分のＣａＳＯ４は貯留部１２２内で固体として存在し、ごく一部は貯留部１２２内の水溶液中に溶解する。一方、石灰中に含まれるＭｇＯからは、ＭｇＳＯ４が生成する。従って、貯留部１２２内に貯蔵される水溶液には、ＣａＳＯ４とＭｇＳＯ４とが含まれる。 An absorbent supply pump 124 is provided between the absorbent spray 120 and the reservoir 122. The absorbent supply pump 124 pumps the aqueous solution containing the absorbent in the reservoir 122 into the absorbent spray 120. The pumped aqueous solution containing the absorbent is sprayed from the absorbent spray 120 into the wet desulfurization apparatus 114. Thus, the absorbent and SO 2 reacts, sulfites and sulfates are produced.
For example, in the case of the caustic soda method, NaOH and SO 2 react to become Na 2 SO 3 , and Na 2 SO 4 is generated by reaction with oxygen. Therefore, the aqueous solution stored in the storage unit 122 includes Na 2 SO 3 and Na 2 SO 4 .
In the case of the lime gypsum method, CaSO 4 · 2H 2 O (gypsum) is generated. The solution containing the reaction product is stored in the storage unit 122. Accordingly, the reaction product is circulated in the wet desulfurization apparatus 114. Note that, for example, CaSO 3 is also dissolved in the reservoir 122, but is actively oxidized by the air supplied by the air supply means. Since CaSO 4 is sparingly soluble in water, most of the CaSO 4 exists as a solid in the reservoir 122 and only a small part dissolves in the aqueous solution in the reservoir 122. On the other hand, MgSO 4 is produced from MgO contained in the lime. Therefore, the aqueous solution stored in the storage unit 122 includes CaSO 4 and MgSO 4 .
　湿式脱硫装置１１４の下流側の煙道に、湿式電気集塵装置１１６が設けられても良い。湿式電気集塵装置１１６は、捕集部に常時洗浄水を噴霧し、捕集しきれなかった煤塵やＳＯ３を静電気力によって除去する。湿式電気集塵装置１１６には、中和のためにＮａＯＨ水溶液やＭｇ（ＯＨ）２水溶液といったアルカリ溶液が供給される。このアルカリ溶液は、中和後に排液としてＮａ２ＳＯ４やＭｇＳＯ４といった溶解塩を含む水溶液となる。 A wet electrostatic precipitator 116 may be provided in the flue downstream of the wet desulfurizer 114. The wet electrostatic precipitator 116 always sprays cleaning water on the collecting part, and removes dust and SO 3 that could not be collected by electrostatic force. The wet electrostatic precipitator 116 is supplied with an alkaline solution such as a NaOH aqueous solution or a Mg (OH) 2 aqueous solution for neutralization. This alkaline solution becomes an aqueous solution containing a dissolved salt such as Na 2 SO 4 or MgSO 4 as a drainage solution after neutralization.
　乾式電気集塵装置１１３と湿式脱硫装置１１４との間の煙道１３０に、噴霧手段１４０が設けられる。図２Ａは、煙道１３０の断面を拡大した概略図である。噴霧手段１４０は、溶解塩噴霧配管１４１にノズル１４２が取り付けられた構成とされる。溶解塩噴霧配管１４１は、図２Ａの紙面奥行方向に延在する。図２Ｂに示されるように、溶解塩噴霧配管１４１には、図２Ａの紙面奥行き方向に複数のノズルが取り付けられる。ノズル１４２は、好適には加圧空気により液体を微粒化する二流体ノズルとされる。燃焼排ガスは、溶解塩噴霧配管１４１同士の間を流通する。 Spray means 140 is provided in the flue 130 between the dry electrostatic precipitator 113 and the wet desulfurizer 114. FIG. 2A is an enlarged schematic view of the cross section of the flue 130. The spraying means 140 is configured such that the nozzle 142 is attached to the dissolved salt spray pipe 141. The dissolved salt spray pipe 141 extends in the depth direction of FIG. 2A. As shown in FIG. 2B, a plurality of nozzles are attached to the dissolved salt spray pipe 141 in the depth direction of the paper surface of FIG. 2A. The nozzle 142 is preferably a two-fluid nozzle that atomizes the liquid with pressurized air. The combustion exhaust gas circulates between the dissolved salt spray pipes 141.
　吸収剤供給ポンプ１２４は、貯留部１２２内の溶液を噴霧手段１４０に供給する。あるいは、貯留部１２２に吸収剤供給ポンプ１２４とは別の抜出ポンプが設けられ、抜出ポンプが貯留部１２２内の反応生成物を含む溶液（脱硫排水）を噴霧手段１４０に供給しても良い。なお、石膏石灰法による湿式脱硫装置を適用する場合は、貯留部１２２から噴霧手段１４０に脱硫排水を供給する流路に、Ｎａ２ＳＯ４，ＭｇＳＯ４などの粉体を脱硫排水に供給する溶解塩濃度調整手段が設けられても良い。 The absorbent supply pump 124 supplies the solution in the storage unit 122 to the spray means 140. Alternatively, an extraction pump different from the absorbent supply pump 124 is provided in the storage unit 122, and the extraction pump supplies a solution (desulfurization drainage) containing the reaction product in the storage unit 122 to the spraying unit 140. good. When applying the wet desulfurization system according gypsum lime method, the flow path for supplying desulfurization effluent to the spray means 140 from the reservoir 122, dissolved supplies powder, such as Na 2 SO 4, MgSO 4 in the desulfurization effluent A salt concentration adjusting means may be provided.
　噴霧手段１４０に供給される溶液には、湿式脱硫装置での反応生成物及び吸収剤（ＮａＯＨなど）に由来する溶解塩が含まれる。噴霧手段１４０は、溶液を直径１０～１００μｍ、好ましくは２０～５０μｍ、より好ましくは２５～３５μｍの液滴として煙道１３０中に噴霧する。煙道１３０中には高温の燃焼排ガスが流通する。これにより、噴霧された液滴から水分が蒸発し、微細化され乾燥した溶解塩粒子が生成する。溶解塩粒子に燃焼排ガス中に含まれるＳＯ３が吸着・固定化されて、燃焼排ガス中からＳＯ３が除去される。また、乾燥した溶解塩粒子に含まれる硫酸塩の一部とＳＯ３とが反応する。例えば、Ｎａ２ＳＯ４の一部とＳＯ３により式（１）の反応が進行する。
　　　Ｎａ２ＳＯ４＋ＳＯ３＋２Ｈ２Ｏ→２ＮａＨＳＯ４・Ｈ２Ｏ　・・・（１） The solution supplied to the spraying means 140 includes a reaction product in a wet desulfurization apparatus and a dissolved salt derived from an absorbent (such as NaOH). The spraying means 140 sprays the solution into the flue 130 as droplets having a diameter of 10 to 100 μm, preferably 20 to 50 μm, more preferably 25 to 35 μm. Hot flue gas flows through the flue 130. As a result, the water is evaporated from the sprayed droplets, and refined and dried dissolved salt particles are generated. SO 3 contained in the combustion exhaust gas is adsorbed and fixed to the dissolved salt particles, and SO 3 is removed from the combustion exhaust gas. In addition, a part of the sulfate contained in the dried dissolved salt particles reacts with SO 3 . For example, the reaction of the formula (1) proceeds with a part of Na 2 SO 4 and SO 3 .
Na 2 SO 4 + SO 3 + 2H 2 O → 2NaHSO 4 .H 2 O (1)
　溶液が噴霧される環境は、噴霧された液滴が飛散している間に水分が蒸発する必要があるので、水の蒸発温度以上とされる。また、ＳＯ３と反応させるために、ＳＯ３の露点温度以上とされる。具体的に、１３０℃以上、好ましくは１４０℃以上とされる。 The environment in which the solution is sprayed is set to be equal to or higher than the evaporation temperature of water because the water needs to evaporate while the sprayed droplets are scattered. Furthermore, to react with SO 3, it is more dew point of SO 3. Specifically, the temperature is 130 ° C. or higher, preferably 140 ° C. or higher.
　図３Ａおよび図３Ｂに、噴霧手段の別の形態を示す。図３Ａは、噴霧手段１４０の断面図であり、溶解塩噴霧配管１４１の上部に噴霧手段洗浄部１５０が設置される。噴霧手段洗浄部１５０は、噴霧手段洗浄用配管１５１と排出孔１５２とで構成される。排出孔１５２から噴霧手段１４０の溶解塩噴霧配管１４１に向かって、洗浄水が排出される。図３Ｂに示されるように、噴霧手段洗浄用配管１５１は溶解塩噴霧配管１４１に対して平行に配置され、噴霧手段洗浄用配管１５１の延在方向に複数の排出孔１５２が設けられる。 3A and 3B show another form of spraying means. FIG. 3A is a cross-sectional view of the spraying means 140, and the spraying means cleaning unit 150 is installed on the upper part of the dissolved salt spray pipe 141. The spraying means cleaning unit 150 includes a spraying means cleaning pipe 151 and a discharge hole 152. The washing water is discharged from the discharge hole 152 toward the dissolved salt spray pipe 141 of the spray means 140. As shown in FIG. 3B, the spraying means cleaning pipe 151 is arranged in parallel to the dissolved salt spraying pipe 141, and a plurality of discharge holes 152 are provided in the extending direction of the spraying means cleaning pipe 151.
　排出孔１５２から洗浄水が排出される。排出された洗浄水は、溶解塩噴霧配管１４１の外壁を伝って流れる。これにより、噴霧手段洗浄用配管１５１の外壁に乾燥した溶解塩が付着することが防止される。この結果、溶解塩噴霧配管１４１同士の間に溶解塩が付着・堆積して燃焼排ガスの流路面積が減少することを防止することができる。排出孔１５２からの洗浄水の排出は、間欠的に行っても良いし、連続的に行っても良い。
　噴霧手段洗浄用配管１５１に供給される洗浄水は、工業用水、湿式脱硫装置１１４の脱硫排水及び湿式電気集塵装置１１６の中和排水のいずれか、あるいはこれらのうち２種以上が混合された水とされる。洗浄水を脱硫排水及び中和排水を使用することにより、排ガス処理装置の運転コストを低減することができる。 Wash water is discharged from the discharge hole 152. The discharged wash water flows along the outer wall of the dissolved salt spray pipe 141. This prevents the dried dissolved salt from adhering to the outer wall of the spraying means cleaning pipe 151. As a result, it is possible to prevent the dissolved salt from adhering and depositing between the dissolved salt spray pipes 141 and reducing the flow area of the combustion exhaust gas. The discharge of the washing water from the discharge hole 152 may be performed intermittently or continuously.
The cleaning water supplied to the spraying means cleaning pipe 151 is either industrial water, desulfurization effluent of the wet desulfurization apparatus 114 and neutralization effluent of the wet electrostatic precipitator 116, or a mixture of two or more of these. It is made with water. By using desulfurization effluent and neutralization effluent as the washing water, the operating cost of the exhaust gas treatment device can be reduced.
　本実施形態では、湿式脱硫装置１１４と乾式電気集塵装置１１３との間の煙道１３０の周方向に沿って、壁面洗浄用配管１６０が設けられる。壁面洗浄用配管１６０には、図２Ａに示されるように、煙道の周方向に複数の孔１６１が設けられる。 In this embodiment, the wall surface cleaning pipe 160 is provided along the circumferential direction of the flue 130 between the wet desulfurization apparatus 114 and the dry electrostatic precipitator 113. As shown in FIG. 2A, the wall cleaning pipe 160 is provided with a plurality of holes 161 in the circumferential direction of the flue.
　壁面洗浄用配管１６０の孔１６１から、壁面洗浄水が煙道１３０の壁面１３１に向かって連続的に供給される。これにより、周囲の排ガス温度を低下させず、壁面１３１に壁面洗浄水の液膜が形成される。壁面洗浄水を供給しない場合に煙道の溶解塩粒子が付着する領域の全面に渡って液膜が形成されるように、壁面洗浄用配管１６０の設置位置及び設置数が設定される。例えば、図１及び図２では噴霧手段１４０の下流側の壁面１３１にそれぞれ２本または１本の壁面洗浄用配管１６０が設置されている。また、壁面洗浄用配管１６０に設けられる孔１６１の数、間隔及び壁面に対する角度や、孔１６１の大きさは、溶解塩粒子が付着する領域の全面に渡って液膜が形成されるように、適宜設定される。 Wall cleaning water is continuously supplied from the hole 161 of the wall cleaning pipe 160 toward the wall 131 of the flue 130. Thereby, the liquid film of the wall surface cleaning water is formed on the wall surface 131 without lowering the temperature of the surrounding exhaust gas. When the wall surface cleaning water is not supplied, the installation position and the number of the wall surface cleaning pipes 160 are set so that a liquid film is formed over the entire surface of the flue where the dissolved salt particles adhere. For example, in FIGS. 1 and 2, two or one wall cleaning pipe 160 is installed on the wall surface 131 on the downstream side of the spraying means 140. In addition, the number of holes 161 provided in the wall surface cleaning pipe 160, the interval and the angle with respect to the wall surface, and the size of the holes 161 are such that a liquid film is formed over the entire area where the dissolved salt particles adhere. Set as appropriate.
　煙道１３０は、ダクト用板の煙道外側に、Ｃ型鋼やＬ字型鋼の外部補強材が溶接されて構成されている。煙道を間欠的に洗浄すると、壁面１３１は温度高－低を繰り返し、外部補強材の溶接部に熱応力が繰り返し印加される。これにより、壁面１３１と外部補強材との溶接部に割れが発生する。本実施形態のように常時洗浄水の液膜を形成することにより、熱応力による煙道の損傷発生を防止することができる。 The flue 130 is configured by welding an external reinforcing material such as C-shaped steel or L-shaped steel to the outside of the flue of the duct plate. When the flue is cleaned intermittently, the wall surface 131 repeats high and low temperatures, and thermal stress is repeatedly applied to the welded portion of the external reinforcing material. Thereby, a crack generate | occur | produces in the welding part of the wall surface 131 and an external reinforcement material. By always forming a liquid film of cleaning water as in this embodiment, it is possible to prevent flue damage from being caused by thermal stress.
　壁面洗浄水は、工業用水、湿式脱硫装置１１４の脱硫排水及び湿式電気集塵装置１１６の中和排水のいずれか、あるいはこれらのうち２種以上が混合された水とされる。こうすることで、排ガス処理装置の運転コストを低減することができる。
　壁面洗浄水は、煙道１３０の壁面を伝い、湿式脱硫装置１１４に流入する。 The wall surface washing water is either industrial water, desulfurization effluent of the wet desulfurization device 114, or neutralization effluent of the wet electrostatic precipitator 116, or water in which two or more of these are mixed. By doing so, the operating cost of the exhaust gas treatment apparatus can be reduced.
The wall surface cleaning water flows along the wall surface of the flue 130 and flows into the wet desulfurization apparatus 114.
＜第２実施形態＞
　図４は、第２実施形態に係る排ガス処理装置の概略図である。排ガス処理装置２００は壁面洗浄水を回収・循環させる回収部及び循環部が設置されており、その他の構成は第１実施形態と同様とされる。本実施形態において、湿式脱硫装置２１４は石膏石灰法を採用したものとされる。
　具体的に、湿式脱硫装置２１４と乾式電気集塵装置２１３との間の煙道２３０に、第１実施形態と同様に噴霧手段２４０及び壁面洗浄用配管２６０が設置される。壁面洗浄用配管２６０の下方に、回収部２８０が、壁面洗浄用配管２６０と同様に煙道２３０の周方向に沿って設置される。回収部２８０は例えば樋状の流通路とされる。
　回収部２８０は循環部２９０に接続される。循環部２９０は煙道２３０の外側に設置され、壁面洗浄水タンク２９１及び壁面洗浄水供給ポンプ２９２を備える。 Second Embodiment
FIG. 4 is a schematic view of an exhaust gas treatment apparatus according to the second embodiment. The exhaust gas treatment apparatus 200 is provided with a collection unit and a circulation unit for collecting and circulating the wall surface cleaning water, and other configurations are the same as those of the first embodiment. In the present embodiment, the wet desulfurization apparatus 214 adopts a gypsum lime method.
Specifically, the spray means 240 and the wall surface cleaning pipe 260 are installed in the flue 230 between the wet desulfurization apparatus 214 and the dry electrostatic precipitator 213 as in the first embodiment. Below the wall surface cleaning pipe 260, the recovery unit 280 is installed along the circumferential direction of the flue 230, similarly to the wall surface cleaning pipe 260. The collection unit 280 is, for example, a bowl-shaped flow path.
The collection unit 280 is connected to the circulation unit 290. The circulation unit 290 is installed outside the flue 230 and includes a wall surface cleaning water tank 291 and a wall surface cleaning water supply pump 292.
　壁面洗浄用配管２６０から、壁面洗浄水が煙道２３０の壁面に向かって連続的に供給され、壁面洗浄水が煙道２３０の壁面に液膜を形成しながら流れ落ちる。流れ落ちた壁面洗浄水は、回収部２８０で回収される。回収された壁面洗浄水は、壁面洗浄水タンク２９１に搬送され、貯留される。
　壁面洗浄水タンク２９１内の壁面洗浄水は、壁面洗浄水供給ポンプ２９２により汲み上げられ、壁面洗浄用配管２６０に循環される。 Wall surface cleaning water is continuously supplied from the wall surface cleaning pipe 260 toward the wall surface of the flue 230, and the wall surface cleaning water flows down while forming a liquid film on the wall surface of the flue 230. The wall surface washing water that has flowed down is collected by the collection unit 280. The collected wall surface washing water is transferred to the wall surface washing water tank 291 and stored.
The wall surface cleaning water in the wall surface cleaning water tank 291 is pumped up by the wall surface cleaning water supply pump 292 and circulated through the wall surface cleaning pipe 260.
　図４において、壁面洗浄水タンク２９１に、洗浄水補給部２９３及びｐＨ調整剤供給部２９４が接続される。また、壁面洗浄水タンク２９１には攪拌装置２９５が設けられる。
　蒸発などにより回収される壁面洗浄水が減少して壁面洗浄水タンクの貯留量が低下した場合、洗浄水補給部２９３は壁面洗浄水を壁面洗浄水タンクに補給する。補給される壁面洗浄水は、工業用水、湿式電気集塵装置２１６からの中和排水、あるいは、これらの混合溶液とされる。
　壁面洗浄水がＳＯ２やＳＯ３を吸収して回収される壁面洗浄水のｐＨが低下した場合、ｐＨ調整剤供給部２９４はｐＨ調整剤を壁面洗浄水タンク２９１に供給する。壁面洗浄水のｐＨは、中性程度に調整される。ｐＨ調整剤は、ＮａＯＨ、Ｍｇ（ＯＨ）２、ＣａＯなどの水溶液とされる。 In FIG. 4, a cleaning water supply unit 293 and a pH adjuster supply unit 294 are connected to the wall surface cleaning water tank 291. The wall surface washing water tank 291 is provided with a stirring device 295.
When the wall surface cleaning water collected by evaporation or the like decreases and the storage amount of the wall surface cleaning water tank decreases, the cleaning water supply unit 293 supplies the wall surface cleaning water to the wall surface cleaning water tank. The wall surface cleaning water to be replenished is industrial water, neutralized waste water from the wet electrostatic precipitator 216, or a mixed solution thereof.
When the wall surface cleaning water that has been recovered by absorbing SO 2 or SO 3 has lowered in pH, the pH adjusting agent supply unit 294 supplies the pH adjusting agent to the wall surface cleaning water tank 291. The pH of the wall surface cleaning water is adjusted to a neutral level. The pH adjuster is an aqueous solution such as NaOH, Mg (OH) 2 , or CaO.
　本実施形態では、図４に示されるように、回収部２８０の下部に回収部洗浄手段２８１を設置しても良い。回収部洗浄手段２８１は、例えばスプレーとされる。
　壁面洗浄水供給ポンプ２９２で汲み上げられた壁面洗浄水の一部は、回収部洗浄手段２８１に供給される。回収部洗浄手段２８１は、回収部２８０の外壁に洗浄水を間欠的に噴射する。これにより、回収部２８０の外壁に溶解塩が付着して腐食するのを防止することができる。噴射された洗浄水は、湿式脱硫装置２１４に流入する。 In the present embodiment, as shown in FIG. 4, a recovery unit cleaning unit 281 may be installed below the recovery unit 280. The collection unit cleaning unit 281 is, for example, a spray.
A part of the wall surface cleaning water pumped up by the wall surface cleaning water supply pump 292 is supplied to the recovery unit cleaning means 281. The recovery unit cleaning means 281 intermittently injects cleaning water onto the outer wall of the recovery unit 280. Thereby, it can prevent that dissolved salt adheres to the outer wall of the collection | recovery part 280, and it corrodes. The sprayed cleaning water flows into the wet desulfurization device 214.
　１００，２００　排ガス処理装置
　１１３，２１３　乾式電気集塵装置
　１１４，２１４　湿式脱硫装置
　１１６，２１６　湿式電気集塵装置
　１３０，２３０　煙道
　１４０，２４０　噴霧手段
　１５０　噴霧手段洗浄部
　１６０，２６０　壁面洗浄用配管
　２８０　回収部
　２９０　循環部 100,200 Exhaust gas treatment equipment 113,213 Dry type electrostatic precipitator 114,214 Wet desulfurization equipment 116,216 Wet electrostatic precipitator 130,230 Flue 140,240 Spraying means 150 Spraying means cleaning part 160,260 Wall surface cleaning pipe 280 Recovery unit 290 Circulation unit

Claims (11)

  1. 　燃焼排ガス中に含まれるＳＯ３を除去する排ガス処理装置であって、
    　湿式脱硫装置の上流側の煙道に溶解塩を含む水溶液を噴霧する噴霧手段と、
    　前記煙道の壁面の周方向に沿って、前記煙道の壁面に対して壁面洗浄水を供給し、前記煙道の前記溶解塩が付着する領域の全面に前記壁面洗浄水の液膜を形成するための壁面洗浄配管とを備える排ガス処理装置。     An exhaust gas treatment apparatus for removing SO 3 contained in combustion exhaust gas,
    Spray means for spraying an aqueous solution containing a dissolved salt on the flue upstream of the wet desulfurization apparatus;
    Wall cleaning water is supplied to the wall of the flue along the circumferential direction of the wall of the flue, and a liquid film of the wall cleaning water is formed on the entire surface of the flue to which the dissolved salt adheres. An exhaust gas treatment apparatus comprising a wall surface cleaning pipe.
  2. 　前記壁面洗浄水が、前記湿式脱硫装置の脱硫排水とされる請求項１に記載の排ガス処理装置。 The exhaust gas treatment apparatus according to claim 1, wherein the wall surface cleaning water is desulfurization waste water of the wet desulfurization apparatus.
  3. 　前記湿式脱硫装置の後段に湿式電気集塵装置が設けられ、前記壁面洗浄水が、前記湿式電気集塵装置の排水とされる請求項１に記載の排ガス処理装置。 The exhaust gas treatment apparatus according to claim 1, wherein a wet electrostatic precipitator is provided downstream of the wet desulfurization apparatus, and the wall surface washing water is used as wastewater of the wet electrostatic precipitator.
  4. 　前記噴霧手段の上部に、前記噴霧手段を洗浄する噴霧手段洗浄水を供給する噴霧手段洗浄配管が設けられる請求項１に記載の排ガス処理装置。 The exhaust gas treatment apparatus according to claim 1, wherein a spray means cleaning pipe for supplying spray means cleaning water for cleaning the spray means is provided at an upper portion of the spray means.
  5. 　前記噴霧手段洗浄水が、前記湿式脱硫装置の脱硫排水とされる請求項４に記載の排ガス処理装置。 The exhaust gas treatment apparatus according to claim 4, wherein the spray means washing water is desulfurization waste water of the wet desulfurization apparatus.
  6. 　前記湿式脱硫装置の後段に湿式電気集塵装置が設けられ、前記噴霧手段洗浄水が、前記湿式電気集塵装置の排水とされる請求項４に記載の排ガス処理装置。 The exhaust gas treatment apparatus according to claim 4, wherein a wet type electrostatic precipitator is provided at a subsequent stage of the wet desulfurization unit, and the spray means washing water is used as a waste water of the wet type electrostatic precipitator.
  7. 　前記壁面洗浄配管の下方の前記壁面の周方向に沿って設けられ、前記壁面洗浄水を回収する回収部と、
    　該回収部で回収された前記壁面洗浄水を、前記壁面洗浄配管に循環させる循環部とを備える請求項１乃至請求項３のいずれかに記載の排ガス処理装置。     A recovery unit that is provided along a circumferential direction of the wall surface below the wall surface cleaning pipe, and that recovers the wall surface cleaning water;
    The exhaust gas treatment apparatus according to any one of claims 1 to 3, further comprising a circulation unit configured to circulate the wall surface cleaning water recovered by the recovery unit through the wall surface cleaning pipe.
  8. 　前記回収された壁面洗浄水に、アルカリを供給するアルカリ供給部を備える請求項７に記載の排ガス処理装置。 The exhaust gas treatment apparatus according to claim 7, further comprising an alkali supply unit that supplies alkali to the collected wall surface washing water.
  9. 　燃焼排ガス中に含まれるＳＯ３を除去する排ガス処理方法であって、
    　湿式脱硫装置の上流側の煙道に、溶解塩を含む水溶液を噴霧するとともに、
    　前記煙道の壁面に対して壁面洗浄水が供給され、前記煙道の前記溶解塩が付着する領域の全面に、前記壁面洗浄水の液膜が形成される排ガス処理方法。     An exhaust gas treatment method for removing SO 3 contained in combustion exhaust gas,
    While spraying an aqueous solution containing dissolved salt on the flue upstream of the wet desulfurization unit,
    An exhaust gas treatment method in which wall surface wash water is supplied to the wall surface of the flue, and a liquid film of the wall surface wash water is formed on the entire surface of the flue to which the dissolved salt adheres.
  10. 　噴霧手段洗浄水が供給されて、前記噴霧手段が洗浄される請求項９に記載の排ガス処理方法。 10. The exhaust gas treatment method according to claim 9, wherein spraying means cleaning water is supplied to clean the spraying means.
  11. 　前記壁面洗浄水を回収し、前記壁面洗浄水として再循環させる請求項９に記載の排ガス処理方法。 The exhaust gas treatment method according to claim 9, wherein the wall surface cleaning water is collected and recirculated as the wall surface cleaning water.
PCT/JP2011/061105 2010-05-17 2011-05-13 Exhaust-gas treatment device and exhaust-gas treatment method WO2011145534A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2010-113027 2010-05-17
JP2010113027A JP5754892B2 (en) 2010-05-17 2010-05-17 Exhaust gas treatment apparatus and exhaust gas treatment method

Publications (1)

Publication Number Publication Date
WO2011145534A1 true WO2011145534A1 (en) 2011-11-24

Family

ID=44991640

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2011/061105 WO2011145534A1 (en) 2010-05-17 2011-05-13 Exhaust-gas treatment device and exhaust-gas treatment method

Country Status (2)

Country Link
JP (1) JP5754892B2 (en)
WO (1) WO2011145534A1 (en)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2012153838A1 (en) * 2011-05-12 2012-11-15 三菱重工メカトロシステムズ株式会社 Exhaust gas treatment method and exhaust gas treatment device
EP3388136A4 (en) * 2015-12-07 2019-08-07 Chiyoda Corporation Flue gas desulfurization apparatus
CN113828136A (en) * 2021-10-15 2021-12-24 上海电气集团股份有限公司 Flue gas treatment system and treatment method

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5871376B2 (en) * 2012-01-13 2016-03-01 前澤化成工業株式会社 Microbial fuel cell
SG10202003942VA (en) * 2017-03-28 2020-05-28 Mitsubishi Hitachi Power Sys Ship desulfurization device, hull integrated desulfurization device, ship, and method for assembling hull integrated desulfurization device to ship
CN108452634B (en) * 2018-06-14 2024-04-02 济南众焦先科环保科技有限公司 Organic waste gas treatment process and equipment

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS50119637U (en) * 1974-03-18 1975-09-30
JPS5183075A (en) * 1975-01-20 1976-07-21 Babcock Hitachi Kk SUKEERINGUBOSHIHOHO
JP2006326575A (en) * 2005-04-26 2006-12-07 Mitsubishi Heavy Ind Ltd Device and method of treating exhaust gas
JP2007296447A (en) * 2006-04-28 2007-11-15 Babcock Hitachi Kk Two-chamber type wet flue gas desulfurization apparatus

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH09141048A (en) * 1995-11-27 1997-06-03 Babcock Hitachi Kk Wet flue gas desulfurizing method and device therefor

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS50119637U (en) * 1974-03-18 1975-09-30
JPS5183075A (en) * 1975-01-20 1976-07-21 Babcock Hitachi Kk SUKEERINGUBOSHIHOHO
JP2006326575A (en) * 2005-04-26 2006-12-07 Mitsubishi Heavy Ind Ltd Device and method of treating exhaust gas
JP2007296447A (en) * 2006-04-28 2007-11-15 Babcock Hitachi Kk Two-chamber type wet flue gas desulfurization apparatus

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2012153838A1 (en) * 2011-05-12 2012-11-15 三菱重工メカトロシステムズ株式会社 Exhaust gas treatment method and exhaust gas treatment device
EP3388136A4 (en) * 2015-12-07 2019-08-07 Chiyoda Corporation Flue gas desulfurization apparatus
US10661222B1 (en) 2015-12-07 2020-05-26 Chyoda Corporation Flue gas desulfurization system
CN113828136A (en) * 2021-10-15 2021-12-24 上海电气集团股份有限公司 Flue gas treatment system and treatment method
CN113828136B (en) * 2021-10-15 2024-04-12 上海电气集团股份有限公司 Flue gas treatment system and method

Also Published As

Publication number Publication date
JP5754892B2 (en) 2015-07-29
JP2011240226A (en) 2011-12-01

Similar Documents

Publication Publication Date Title
WO2011145534A1 (en) Exhaust-gas treatment device and exhaust-gas treatment method
JP4920993B2 (en) Exhaust gas treatment apparatus and exhaust gas treatment method
JP5984712B2 (en) Exhaust gas treatment system and exhaust gas treatment method
WO2014038354A1 (en) Desulfurization device, and soot removal system
CN101956991B (en) Process and device for dehumidifying wet flue gas purification tail gas
JP6230818B2 (en) Exhaust gas treatment apparatus and exhaust gas treatment method
JP2008246406A (en) Waste gas treatment device and waste gas treatment method
WO2011016584A1 (en) Device for treating exhaust gas
JP5284722B2 (en) Flue gas denitration equipment
CN103547355A (en) Spray drying apparatus for filtrate from desulfurization waste water, and exhaust gas treatment system
JP2012187476A (en) Exhaust gas treatment equipment and exhaust gas treatment method
JPWO2008087769A1 (en) Wet flue gas desulfurization equipment
WO2003000387A1 (en) So3 separating and removing equipment for flue gas
CN100553745C (en) Reverse flow type seawater desulfurizing and absorption tower
CN100475316C (en) Exhaust gas treatment device and exhaust gas treatment method
JP2010269277A (en) Method and apparatus of suppressing mercury re-release in desulfurization apparatus
JP6062463B2 (en) Exhaust gas treatment method and exhaust gas treatment apparatus
JP5859244B2 (en) Smoke exhaust treatment equipment and smoke exhaust treatment method
WO2012153838A1 (en) Exhaust gas treatment method and exhaust gas treatment device
JP2004261766A (en) Wet bag filter apparatus
CN105396451B (en) Caustic dip efficient removal SO in a kind of spray desulfurizing tower3Technique
CZ62398A3 (en) Process of treating combustion products and apparatus for making the same
CN201244442Y (en) Spraying tube
CN103406011B (en) A kind of equipment of pesticides packaging castoff burning vent gas treatment
CN208553709U (en) Flue gas washing system

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 11783468

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 11783468

Country of ref document: EP

Kind code of ref document: A1