JP2003144849A - Exhaust gas desulfurization system and method therefor - Google Patents
Exhaust gas desulfurization system and method thereforInfo
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- JP2003144849A JP2003144849A JP2001349808A JP2001349808A JP2003144849A JP 2003144849 A JP2003144849 A JP 2003144849A JP 2001349808 A JP2001349808 A JP 2001349808A JP 2001349808 A JP2001349808 A JP 2001349808A JP 2003144849 A JP2003144849 A JP 2003144849A
- Authority
- JP
- Japan
- Prior art keywords
- sulfuric acid
- flue gas
- gas desulfurization
- concentration
- exhaust gas
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、石炭や重油等の燃
料を燃焼させるボイラ、ガスタービン、エンジンや焼却
炉等から排出される排ガス中の硫黄酸化物（ＳＯｘ）を
除去するための排煙脱硫システムに関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a flue gas for removing sulfur oxides (SOx) in exhaust gas discharged from a boiler burning a fuel such as coal or heavy oil, a gas turbine, an engine or an incinerator. Regarding desulfurization system.
【０００２】[0002]
【背景技術】従来、排ガス中の硫黄酸化物の除去方法と
して、石灰石または消石灰スラリーを吸収剤として用い
て、排ガス中の硫黄分を石膏として回収する石灰−石膏
法が採用されている。他の方法としては、乾式法の活性
炭による吸着法が知られている。BACKGROUND ART Conventionally, as a method for removing sulfur oxides in exhaust gas, a lime-gypsum method has been adopted in which limestone or slaked lime slurry is used as an absorbent and the sulfur content in the exhaust gas is recovered as gypsum. As another method, a dry method of adsorption with activated carbon is known.
【０００３】上記従来の石灰−石膏法では、石灰石また
は消石灰スラリーを排ガス中にスプレーすることによ
り、排ガスの増湿冷却及びＳＯx の吸収を同時に行って
いる。このため、多量のスラリーを循環する必要があ
り、スラリーを循環するための動力及び多量の水が必要
となる。In the above-mentioned conventional lime-gypsum method, limestone or slaked lime slurry is sprayed into the exhaust gas to simultaneously perform humidification cooling of the exhaust gas and absorption of SOx. Therefore, it is necessary to circulate a large amount of slurry, and power and a large amount of water for circulating the slurry are required.
【０００４】一方、乾式法の場合、活性炭に吸着した硫
黄分を加熱によって脱離させるため、大量の熱を必要と
する。しかも、この方法の場合、生成した希硫酸の廃棄
や、吸着材の損耗等が問題になる。したがって、本発明
の目的は、硫黄酸化物の吸収剤や大型の脱硫設備を必要
とせず、しかも脱硫の際に高い濃度の硫酸を得ることの
できる脱硫装置を提供することにある。On the other hand, in the dry method, a large amount of heat is required because the sulfur content adsorbed on the activated carbon is desorbed by heating. Moreover, in the case of this method, disposal of the generated dilute sulfuric acid, wear of the adsorbent, and the like pose problems. Therefore, an object of the present invention is to provide a desulfurization apparatus which does not require a sulfur oxide absorbent or a large-scale desulfurization facility and can obtain a high concentration of sulfuric acid during desulfurization.
【０００５】このため、排ガス中のＳＯｘを除去する装
置として活性炭素繊維等の多孔質炭素材料に排ガス中の
ＳＯｘを吸着させ、多孔質炭素材料の触媒作用を利用し
て排ガス中に含まれる酸素により硫黄成分を酸化させ、
これを水分に吸収させて硫酸として多孔質炭素材料から
除去することが提案されている（特開平１１−３４７３
５０号公報参照）。Therefore, as a device for removing SOx in exhaust gas, SOx in exhaust gas is adsorbed on a porous carbon material such as activated carbon fiber, and oxygen contained in the exhaust gas is utilized by utilizing the catalytic action of the porous carbon material. To oxidize the sulfur component,
It has been proposed to absorb this in water and remove it as sulfuric acid from the porous carbon material (JP-A-11-3473).
No. 50).
【０００６】この活性炭素繊維を用いた従来の排煙処理
装置では、排ガス中のＳＯｘを吸着するための活性炭素
繊維槽を吸着塔内に配設し、排ガスを供給して活性炭素
繊維の表面でＳＯ2 をＳＯ3 に酸化し、生成したＳＯ3
が供給された水と反応して、硫酸（Ｈ2 ＳＯ4 ）を生成
するようにしている。In the conventional flue gas treatment equipment using this activated carbon fiber, an activated carbon fiber tank for adsorbing SOx in the exhaust gas is arranged in the adsorption tower, and the exhaust gas is supplied to the surface of the activated carbon fiber. SO 3 to the in SO 2 oxidation to SO 3, generated
Reacts with the supplied water to produce sulfuric acid (H 2 SO 4 ).
【０００７】ここで、脱硫により得られた硫酸はその
後、濃縮して所定濃度の硫酸としたり、石灰スラリーと
反応させて石膏スラリーとし、石膏を得るようにしてい
る。Here, the sulfuric acid obtained by desulfurization is then concentrated to form sulfuric acid having a predetermined concentration or reacted with lime slurry to form gypsum slurry to obtain gypsum.
【０００８】ところで、脱硫装置からの硫酸は運転条件
や排ガスの状態により脱硫装置から排出される硫酸の濃
度に差があり、ある一定濃度以下の硫酸では石膏を生成
させても石膏を分離回収することが困難になるという問
題がある。このため、従来では、石膏製造能力がない低
濃度の硫酸は産業廃棄物として処理する必要があるとい
う問題がある。By the way, the sulfuric acid from the desulfurizer has a difference in the concentration of the sulfuric acid discharged from the desulfurizer depending on the operating conditions and the state of the exhaust gas, and if the sulfuric acid has a certain concentration or less, the gypsum is separated and recovered even if gypsum is produced. There is a problem that it becomes difficult. Therefore, conventionally, there is a problem that it is necessary to treat low-concentration sulfuric acid having no gypsum production capacity as industrial waste.
【０００９】また、石膏を製造することなく希硫酸を製
造する場合においても、あまりにも低濃度であると、濃
縮設備の大型化となり、硫酸製造設備のコストが増大す
るという問題がある。Further, even when dilute sulfuric acid is produced without producing gypsum, if the concentration is too low, the concentration equipment becomes large and the cost of the sulfuric acid production equipment increases.
【００１０】本発明は、上記問題に鑑み、産業廃棄物の
排出を無くし、効率的な排煙脱硫システムを提供するこ
とを課題とする。In view of the above problems, it is an object of the present invention to provide an efficient flue gas desulfurization system that eliminates the discharge of industrial waste.
【００１１】[0011]
【課題を解決するための手段】前述した課題を解決する
第１の発明は、硫黄酸化物を含有する排ガスが流通する
装置塔内に設けられ、活性炭素繊維層で形成される触媒
層と、上記装置塔内に設けられ、上記触媒層に硫酸生成
用の添加水を供給する水供給手段と、上記装置塔外部又
は内部で排ガスを冷却すると共に増湿する増湿冷却手段
とからなる排煙脱硫装置と、該排煙脱硫装置からの希硫
酸と石灰スラリーとを反応させ、石膏スラリーを得る石
膏反応槽と、該石膏反応槽により得られた石膏スラリー
から水分を分離して石膏を得る脱水器とを備えた排煙脱
硫システムであって、上記排煙脱硫装置から排出される
硫酸の濃度を計測する硫酸濃度計と、硫酸濃度計の判定
結果により硫酸排出ラインを切替える流路切替手段とを
備えたことを特徴とする排煙脱硫システムにある。A first invention for solving the above-mentioned problems is to provide a catalyst layer formed in an activated carbon fiber layer, which is provided in an apparatus tower through which exhaust gas containing sulfur oxide flows. Exhaust smoke consisting of water supply means provided in the equipment tower and supplying additive water for sulfuric acid generation to the catalyst layer, and humidification cooling means for cooling exhaust gas outside or inside the equipment tower and increasing the humidity Desulfurization equipment, dilute sulfuric acid from the flue gas desulfurization equipment and lime slurry are reacted to obtain a gypsum slurry gypsum reaction tank, and water is separated from the gypsum slurry obtained by the gypsum reaction tank to obtain gypsum dehydration A flue gas desulfurization system including a vessel, a sulfuric acid concentration meter that measures the concentration of sulfuric acid discharged from the flue gas desulfurization device, and a flow path switching means that switches the sulfuric acid discharge line according to the determination result of the sulfuric acid concentration meter. It is equipped with In the flue gas desulfurization system.
【００１２】第２の発明は、硫黄酸化物を含有する排ガ
スが流通する装置塔内に設けられ、活性炭素繊維層で形
成される触媒層と、上記装置塔内に設けられ、上記触媒
層に硫酸生成用の添加水を供給する水供給手段と、上記
装置塔外部又は内部で排ガスを冷却すると共に増湿する
増湿冷却手段とからなる排煙脱硫装置と、上記脱硫装置
で得られた希硫酸を濃縮する濃縮槽とを備えた排煙脱硫
システムであって、上記排煙脱硫装置から排出される硫
酸の濃度を計測する硫酸濃度計と、硫酸濃度計の判定結
果により硫酸排出ラインを切替える切替手段とを備えた
ことを特徴とする排煙脱硫システムにある。A second aspect of the present invention is a catalyst layer which is provided in an apparatus tower through which an exhaust gas containing sulfur oxides flows and which is formed of an activated carbon fiber layer, and the catalyst layer which is provided in the apparatus tower. A flue gas desulfurization device consisting of a water supply means for supplying added water for sulfuric acid generation, and a humidification cooling means for cooling and humidifying exhaust gas outside or inside the apparatus tower, and a rare gas obtained by the desulfurization apparatus. A flue gas desulfurization system having a concentration tank for concentrating sulfuric acid, wherein a sulfuric acid concentration meter for measuring the concentration of sulfuric acid discharged from the flue gas desulfurization device and a sulfuric acid discharge line are switched depending on the judgment result of the sulfuric acid concentration meter. A flue gas desulfurization system characterized by comprising switching means.
【００１３】第３の発明は、第１又は２の発明におい
て、上記硫酸排出ラインの切替が、判定値以上の場合に
は硫酸の送液を石膏反応槽とすると共に、判定値未満の
場合には、硫酸の送液を増湿冷却装置又は水供給手段の
いずれか一方又は両方とすることを特徴とする排煙脱硫
システムにある。In a third aspect of the invention, in the first or second aspect, when the switching of the sulfuric acid discharge line is equal to or more than the determination value, the sulfuric acid is sent to the gypsum reaction tank, and when the determination value is less than the determination value. Is a flue gas desulfurization system characterized in that one or both of a humidification cooling device and a water supply means feed sulfuric acid.
【００１４】第４の発明は、第１乃至３のいずれか一の
発明において、上記硫酸濃度計が硫酸流入ラインと硫酸
排出ラインとを備えた所定容積の計測槽と、該計測槽の
重量を測定する秤とを具備してなり、硫酸を連続的に給
液しつつ濃度を計測することを特徴とする排煙脱硫シス
テムにある。According to a fourth aspect of the present invention, in any one of the first to third aspects, the sulfuric acid concentration meter is provided with a measuring tank having a predetermined volume including a sulfuric acid inflow line and a sulfuric acid discharging line, and a weight of the measuring tank. A flue gas desulfurization system comprising a measuring scale and measuring the concentration while continuously supplying sulfuric acid.
【００１５】第５の発明は、第１乃至４のいずれか一の
発明において、上記判定値の硫酸濃度が１％以上である
ことを特徴とする排煙脱硫システムにある。A fifth aspect of the present invention is the flue gas desulfurization system according to any one of the first to fourth aspects of the invention, wherein the sulfuric acid concentration of the determination value is 1% or more.
【００１６】第６の発明は、第１又は２の発明におい
て、排煙脱硫装置が、硫黄酸化物を含有する排ガスの導
入口と該排ガスの排出口を上記装置塔の上部及び下部に
有すると共に、該塔内に設けられた触媒槽層の上方に硫
酸生成用の水の供給器を備えたことを特徴とする排煙脱
硫システムにある。According to a sixth aspect of the present invention, in the flue gas desulfurization apparatus according to the first or second aspect, the exhaust gas containing sulfur oxides has an inlet port and an exhaust port for the exhaust gas in an upper portion and a lower portion of the apparatus tower. The flue gas desulfurization system is characterized in that a water supply device for producing sulfuric acid is provided above the catalyst tank layer provided in the tower.
【００１７】第７の発明は、第１又は２の発明におい
て、上記排ガスがボイラ、ガスタービン、エンジン及び
各種焼却炉から排出されるガスであり、排ガス中の煤塵
を除去する煤塵除去手段を備えてなることを特徴とする
排煙脱硫システムにある。A seventh invention is the fuel cell system according to the first or second invention, wherein the exhaust gas is a gas discharged from a boiler, a gas turbine, an engine and various incinerators, and is provided with a soot / dust removing means for removing soot / dust in the exhaust gas. The flue gas desulfurization system is characterized by the following.
【００１８】第８の発明は、硫黄酸化物を含有する排ガ
スが流通する装置塔内に設けられ、活性炭素繊維層で形
成される触媒層と、上記装置塔内に設けられ、上記触媒
層に硫酸生成用の水を供給する水供給手段とからなる排
煙脱硫装置からの硫酸の濃度を計測し、硫酸濃度が１％
以下の場合には、増湿冷却用の供給水又は触媒水分添加
用の散水として利用すると共に、硫酸濃度が１％を超え
る場合には、石灰スラリーと反応して石膏を得ることを
特徴とする排煙脱硫システムの運転方法にある。An eighth aspect of the present invention is a catalyst layer which is provided in an apparatus tower in which an exhaust gas containing sulfur oxides flows and which is formed of an activated carbon fiber layer, and the catalyst layer which is provided in the apparatus tower. The concentration of sulfuric acid from the flue gas desulfurization unit, which is composed of a water supply means for supplying water for producing sulfuric acid, is measured, and the sulfuric acid concentration is 1%.
In the following cases, it is used as feed water for humidification cooling or sprinkling water for adding catalyst moisture, and when sulfuric acid concentration exceeds 1%, it reacts with lime slurry to obtain gypsum. It is in the operation method of the flue gas desulfurization system.
【００１９】第９の発明は、硫黄酸化物を含有する排ガ
スが流通する装置塔内に設けられ、活性炭素繊維層で形
成される触媒層と、上記装置塔内に設けられ、上記触媒
層に硫酸生成用の水を供給する水供給手段とからなる排
煙脱硫装置からの硫酸の濃度を計測し、硫酸濃度が１％
以下の場合には、増湿冷却用の供給水又は触媒水分添加
用の散水として利用すると共に、硫酸濃度が１％を超え
る場合には硫酸を濃縮することを特徴とする排煙脱硫シ
ステムの運転方法にある。A ninth aspect of the present invention provides a catalyst layer which is provided in an apparatus tower in which an exhaust gas containing sulfur oxides flows and which is formed of an activated carbon fiber layer, and the catalyst layer which is provided in the apparatus tower. The concentration of sulfuric acid from the flue gas desulfurization unit, which is composed of a water supply means for supplying water for producing sulfuric acid, is measured, and the sulfuric acid concentration is 1%.
In the following cases, the flue gas desulfurization system is characterized by being used as feed water for humidification cooling or sprinkling water for adding catalyst moisture, and concentrating sulfuric acid when the sulfuric acid concentration exceeds 1%. On the way.
【００２０】第１０の発明は、硫黄酸化物を含有する排
ガスが流通する装置塔内に設けられ、活性炭素繊維層で
形成される触媒層と、上記装置塔内に設けられ、上記触
媒層に硫酸生成用の水を供給する水供給手段とからなる
排煙脱硫装置からの硫酸の濃度を計測し、硫酸濃度が１
％以下の場合には、増湿冷却用の供給水又は触媒水分添
加用の散水として利用すると共に、硫酸濃度が１％を超
える場合には触媒水分添加用のラインのみ工水に切り替
え、硫酸を増湿冷却用にのみ利用することにより硫酸を
濃縮することを特徴とする排煙脱硫システムの運転方法
にある。A tenth aspect of the invention is to provide a catalyst layer which is provided in an apparatus tower through which an exhaust gas containing sulfur oxide flows and which is formed of an activated carbon fiber layer, and the catalyst layer which is provided in the apparatus tower. The concentration of sulfuric acid from the flue gas desulfurization unit consisting of water supply means for supplying water for producing sulfuric acid was measured, and the sulfuric acid concentration was 1
When it is less than 10%, it is used as feed water for humidification cooling or sprinkling water for adding catalyst moisture, and when the sulfuric acid concentration exceeds 1%, only the catalyst moisture addition line is switched to working water to remove sulfuric acid. It is a method of operating a flue gas desulfurization system characterized by concentrating sulfuric acid by using it only for humidification and cooling.
【００２１】[0021]
【発明の実施の形態】本発明による排煙脱硫装置の実施
の形態を以下に説明するが、本発明はこれらの実施の形
態に限定されるものではない。BEST MODE FOR CARRYING OUT THE INVENTION Embodiments of the flue gas desulfurization apparatus according to the present invention will be described below, but the present invention is not limited to these embodiments.
【００２２】［第１の実施の形態］図１に基づいて排煙
処理装置を備えた排ガス処理システムを説明する。[First Embodiment] An exhaust gas treatment system equipped with a smoke treatment apparatus will be described with reference to FIG.
【００２３】図１の排ガス処理システムは、排ガス中の
硫黄酸化物を脱硫装置での脱硫により硫酸とするもので
ある。図１に示すように、蒸気タービンを駆動する蒸気
を発生させるボイラ１と、該ボイラ１からの排ガス１０
０中の煤塵を除去する除塵機２と、除塵された排ガスを
脱硫塔４内に供給する押込みファン３と、脱硫塔４に供
給する前段で（又は塔内で）排ガス１００を冷却すると
共に増湿を行う増湿冷却装置１６と、触媒層６を内部に
配設し、塔側壁の導入口５から排ガス１００を供給する
と共に、触媒層６の上方から散水ノズル７で水を供給し
て、排ガス中のＳＯｘを希硫酸（Ｈ2 ＳＯ4 ）まで脱硫
反応させる脱硫塔４と、塔部の排出口１２から脱硫され
た浄化排ガスを外部へ排出する煙突１３と、上記脱硫塔
４から排出ポンプ１０を介して硫酸を濃縮する硫酸濃縮
槽５０と、上記脱硫塔４から排出される硫酸の排出ライ
ン６１から分枝され、硫酸の濃度を計測する硫酸濃度計
６２と、該濃度計６２の測定値から硫酸ラインの切替バ
ルブ６３を切替制御する制御手段６４とを具備するもの
である。なお、脱硫塔４から排出される浄化された排ガ
スを排出するラインには必要に応じてミストエリミネー
タ１９を介装し、排ガス中の水分を分離するようにして
もよい。The exhaust gas treatment system shown in FIG. 1 converts sulfur oxides in exhaust gas into sulfuric acid by desulfurization in a desulfurizer. As shown in FIG. 1, a boiler 1 for generating steam for driving a steam turbine and an exhaust gas 10 from the boiler 1 are generated.
The dust remover 2 for removing the soot and dust in the exhaust gas 0, the pushing fan 3 for supplying the exhaust gas from which dust has been removed into the desulfurization tower 4, and the exhaust gas 100 which has been cooled and increased in the preceding stage (or in the tower) for supplying to the desulfurization tower 4. A humidifying and cooling device 16 for humidifying and a catalyst layer 6 are provided inside, and exhaust gas 100 is supplied from an inlet 5 on the side wall of the tower, and water is supplied from above the catalyst layer 6 by a water spray nozzle 7, A desulfurization tower 4 for performing a desulfurization reaction of SOx in exhaust gas to dilute sulfuric acid (H 2 SO 4 ), a chimney 13 for discharging the purified exhaust gas desulfurized from a discharge port 12 of the tower part to the outside, and a discharge pump for the desulfurization tower 4 A sulfuric acid concentration tank 50 for concentrating sulfuric acid via 10, a sulfuric acid concentration meter 62 for branching from a sulfuric acid discharge line 61 discharged from the desulfurization tower 4 and measuring the concentration of sulfuric acid, and measurement of the concentration meter 62. Switch the switching valve 63 of the sulfuric acid line from the value It is intended to and control means 64 for. If necessary, a mist eliminator 19 may be provided in the line for discharging the purified exhaust gas discharged from the desulfurization tower 4 to separate water in the exhaust gas.
【００２４】ここで、上記ボイラ１では、例えば、火力
発電設備の図示しない蒸気タービンを駆動するための蒸
気を発生させるために、石炭や重油等の燃料ｆが炉で燃
焼されるようになっている。ボイラ１の排ガスには硫黄
酸化物（ＳＯｘ )が含有され、排ガスは図示しない脱硝
装置で脱硝されてガスガスヒータで冷却された後に集塵
機２で除塵される。Here, in the boiler 1, for example, in order to generate steam for driving a steam turbine (not shown) of the thermal power generation facility, fuel f such as coal or heavy oil is burned in the furnace. There is. The exhaust gas of the boiler 1 contains sulfur oxides (SOx), and the exhaust gas is denitrated by a denitration device (not shown), cooled by a gas gas heater, and then dedusted by a dust collector 2.
【００２５】上記除塵された排ガス１００は押込みファ
ン３により下部側壁の導入口５から脱硫塔４内に導入さ
れる。脱硫塔４の内部には活性炭素繊維層で形成される
触媒層６が備えられ、該触媒層６には硫酸生成用の水が
水供給手段１７から供給される。水が上部から供給され
た触媒層６の内部に排ガスを下部から通過させることに
より、排ガス１００からＳＯｘを反応除去する。触媒層
６を通過した排ガスは排出口１２から排出され、煙突１
３を通して大気に放出される。The dust-removed exhaust gas 100 is introduced into the desulfurization tower 4 from the inlet 5 on the lower side wall by the pushing fan 3. A catalyst layer 6 formed of an activated carbon fiber layer is provided inside the desulfurization tower 4, and water for sulfuric acid generation is supplied to the catalyst layer 6 from a water supply means 17. SOx is reacted and removed from the exhaust gas 100 by passing the exhaust gas from the lower part into the inside of the catalyst layer 6 supplied with water from the upper part. The exhaust gas that has passed through the catalyst layer 6 is discharged from the discharge port 12 and the stack 1
3 is released to the atmosphere.
【００２６】上記触媒層６は複数の活性炭素繊維層から
なる触媒を備え、各々の活性炭素繊維層の表面では、例
えば、以下の反応により脱硫反応が生じる。この反応メ
カニズムを示す。
ＳＯ2 ＋１／２Ｏ2 ＋Ｈ2 Ｏ→Ｈ2 ＳＯ4 The catalyst layer 6 includes a catalyst composed of a plurality of activated carbon fiber layers, and the desulfurization reaction occurs on the surface of each activated carbon fiber layer, for example, by the following reaction. This reaction mechanism is shown. SO 2 + 1 / 2O 2 + H 2 O → H 2 SO 4
【００２７】上記反応除去された硫酸Ｈ2 ＳＯ4 は希硫
酸となって排出ポンプ１０を介して硫酸タンク１１に排
出される。このようにして、触媒層６の活性炭素繊維層
の中で排ガス１００中の二酸化硫黄ＳＯ2 を吸着して酸
化し、水Ｈ2 Ｏと反応させて硫酸Ｈ2 ＳＯ4 を生成して
離脱除去することにより、排ガス流の脱硫が行われる。The sulfuric acid H 2 SO 4 which has been removed by the above reaction becomes dilute sulfuric acid and is discharged to the sulfuric acid tank 11 via the discharge pump 10. In this way, sulfur dioxide SO 2 in the exhaust gas 100 is adsorbed and oxidized in the activated carbon fiber layer of the catalyst layer 6 and reacted with water H 2 O to generate sulfuric acid H 2 SO 4 and removed and removed. By doing so, the desulfurization of the exhaust gas flow is performed.
【００２８】上記硫酸濃度計６２は既知容積の測定容器
６５と、該容器６５内に硫酸を連続的に供給すると共に
排出する硫酸流入ライン６６及び硫酸排出ライン６７
と、上記容器６５内に供給された硫酸の重さを連続的に
供給する秤６８とを具備するものである。The sulfuric acid concentration meter 62 comprises a measuring container 65 having a known volume, and a sulfuric acid inflow line 66 and a sulfuric acid exhaust line 67 for continuously supplying and discharging sulfuric acid in the container 65.
And a scale 68 for continuously supplying the weight of the sulfuric acid supplied into the container 65.
【００２９】上記硫酸濃度計６２を用いて硫酸濃度を計
測して、硫酸のラインを切替える手法について以下説明
する。A method of measuring the sulfuric acid concentration using the sulfuric acid concentration meter 62 and switching the sulfuric acid line will be described below.
【００３０】図２は硫酸濃度判定のフロー図である。図
２に示すように、脱硫塔４の硫酸溜め部４ａから排出ラ
イン６１により排出された硫酸の一部を硫酸濃度計６２
の測定容器６５内に流入ライン６６を介して連続して供
給する（Ｓ−１１）。上記硫酸濃度計６２の秤６８によ
り硫酸の濃度を連続的に計測する（Ｓ−１２）。次に、
該濃度を制御手段６４において所定の濃度（例えば１％
以上）であるか否かを判定する（Ｓ−１３）。判定の結
果、所定の濃度の判定値（例えば硫酸濃度が１％以上）
であった場合には、切替バルブ６３の切替により、硫酸
濃縮槽５０へ給液するためのラインを切替る（Ｓ−１
４）。一方、判定の結果、所定の濃度の判定値（例えば
硫酸濃度が１％未満）であった場合には、切替バルブ６
３の切替により、増湿冷却装置１６へ給液するためのラ
インを切替る（Ｓ−１５）。この計測を連続的に行うこ
とにより、従来のバッチ式の硫酸濃度の計測のようなタ
イムラグが生じることがなくなる。FIG. 2 is a flow chart for determining the sulfuric acid concentration. As shown in FIG. 2, a part of the sulfuric acid discharged from the sulfuric acid reservoir 4a of the desulfurization tower 4 through the discharge line 61 is partially converted into a sulfuric acid concentration meter 62.
It is continuously supplied into the measurement container 65 through the inflow line 66 (S-11). The sulfuric acid concentration is continuously measured by the scale 68 of the sulfuric acid concentration meter 62 (S-12). next,
The control unit 64 controls the concentration to a predetermined concentration (for example, 1%).
It is determined whether or not the above (S-13). As a result of the judgment, a judgment value of a predetermined concentration (for example, sulfuric acid concentration is 1% or more)
If it is, the line for supplying the liquid to the sulfuric acid concentration tank 50 is switched by switching the switching valve 63 (S-1).
4). On the other hand, as a result of the determination, if the determination value is a predetermined concentration (for example, the sulfuric acid concentration is less than 1%), the switching valve 6
The line for supplying the liquid to the humidification cooling device 16 is switched by switching 3 (S-15). By performing this measurement continuously, there is no time lag as in the conventional batch type sulfuric acid concentration measurement.
【００３１】ここで、本発明で用いる活性炭素繊維の一
例及びその製造例の一例を下記に示す。本発明で用いら
れる活性炭素繊維としては、例えばピッチ系活性炭素繊
維、ポリアクリロニトリル系活性炭素繊維、フェノール
系活性炭素繊維、セルロース系活性炭素繊維を挙げるこ
とができるが、本発明はこれらに限定されるものではな
く、上記触媒作用を奏する活性炭素繊維であれば何等限
定されるものではない。Here, an example of the activated carbon fiber used in the present invention and an example of its production will be shown below. Examples of the activated carbon fiber used in the present invention include pitch-based activated carbon fiber, polyacrylonitrile-based activated carbon fiber, phenol-based activated carbon fiber, and cellulose-based activated carbon fiber, but the present invention is not limited thereto. However, the activated carbon fiber is not limited as long as it is an activated carbon fiber having the above-mentioned catalytic action.
【００３２】［第２の実施の形態］図３に基づいて排煙
処理装置を備えた排ガス処理システムを説明する。[Second Embodiment] An exhaust gas treatment system equipped with a smoke treatment apparatus will be described with reference to FIG.
【００３３】図３の排ガス処理システムは、排ガス中の
硫黄酸化物を脱硫装置での脱硫により硫酸とし、該硫酸
に石灰スラリーを供給して石膏を製造するものである。
図３に示すように、蒸気タービンを駆動する蒸気を発生
させるボイラ１と、該ボイラ１からの排ガス１００中の
煤塵を除去する除塵機２と、除塵された排ガスを脱硫塔
４内に供給する押込みファン３と、脱硫塔内又は塔に供
給する前に排ガス１００を冷却すると共に増湿を行う増
湿冷却装置１６と、触媒層６を内部に配設し、塔下部側
壁の導入口５から排ガス１００を供給すると共に、触媒
層６の上方から散水ノズルで水を供給して、排ガス中の
ＳＯｘを硫酸（Ｈ2 ＳＯ4 ）まで脱硫反応させる脱硫塔
４と、塔頂部の排出口１２から脱硫された浄化排ガスを
外部へ排出する煙突１３と、脱硫塔４から排出ポンプ１
０を介して硫酸（Ｈ2 ＳＯ 4 ）を貯蔵すると共に石灰ス
ラリー５１を供給して石膏を析出させる石膏反応槽５２
と、石膏を沈降させる沈降槽（シックナー）５３と、石
膏スラリー５４から水分を排水（濾液）５７として除去
して石膏５５を得る脱水器５６と、上記脱硫塔４から排
出される硫酸の排出ライン６１から分枝され、硫酸の濃
度を計測する硫酸濃度計６２と、該濃度計６２の測定値
から硫酸ラインの切替バルブ６３を切替制御する制御手
段６４とを具備するものである。また、本実施の形態に
おいては、脱硫塔４から排出される硫酸中のＳＳ（浮遊
物質）を沈殿させる静置槽７０を硫酸濃度計６２の全流
側の流入ライン６６に設けている。The exhaust gas treatment system of FIG.
Sulfur oxide is converted to sulfuric acid by desulfurization in a desulfurization device.
The gypsum is manufactured by supplying lime slurry to the.
Generate steam to drive the steam turbine, as shown in Figure 3.
Boiler 1 to be made to exist and in exhaust gas 100 from said boiler 1
Dust remover 2 for removing soot and desulfurization tower
4 and the inside of the desulfurization tower.
Cool the exhaust gas 100 before supplying it and increase the humidity.
The wet cooling device 16 and the catalyst layer 6 are provided inside, and the lower side of the tower
Exhaust gas 100 is supplied from the inlet port 5 of the wall, and the
Water is supplied from above the layer 6 by a watering nozzle,
SOx to sulfuric acid (H2SOFour) To desulfurization tower
4 and the purified exhaust gas desulfurized from the outlet 12 at the top of the tower
A chimney 13 that discharges to the outside and a discharge pump 1 from the desulfurization tower 4
0 through sulfuric acid (H2SO Four) Is stored together with lime
Gypsum reaction tank 52 for supplying rally 51 to deposit gypsum
And a settling tank (thickener) 53 for settling gypsum, and stone
Water is removed from the plaster slurry 54 as waste water (filtrate) 57.
From the desulfurizer 4 and the dehydrator 56 to obtain the gypsum 55
It is branched from the discharge line 61 for the sulfuric acid discharged, and the sulfuric acid is concentrated.
Sulfuric acid densitometer 62 for measuring the degree, and the measured value of the densitometer 62
To control the switching valve 63 of the sulfuric acid line from the
And a stage 64. In addition, in this embodiment
In addition, SS (floating) in the sulfuric acid discharged from the desulfurization tower 4
The static tank 70 for precipitating the
It is provided on the side inflow line 66.
【００３４】図１のシステムでは、脱硫して得られた硫
酸を硫酸のままで使用するものであるが、図３のシステ
ムでは、硫酸に石灰スラリーを供給して石膏スラリーを
得た後、脱水して石膏として利用するものである。In the system of FIG. 1, the sulfuric acid obtained by desulfurization is used as sulfuric acid as it is, but in the system of FIG. 3, lime slurry is supplied to sulfuric acid to obtain gypsum slurry and then dehydrated. It is then used as plaster.
【００３５】本実施の形態によれば、硫酸濃度を計測す
るのに際し、静置槽７０を設けてＳＳ（浮遊物質）を沈
殿させた後に硫酸を連続的に流通させることで、計量容
器内の硫酸の重量・温度を計ることにより比重を求め、
第１の実施の形態よりも高精度な硫酸濃度を計測するよ
うにしている。According to the present embodiment, when measuring the sulfuric acid concentration, the stationary tank 70 is provided to precipitate SS (floating substance) and then the sulfuric acid is continuously circulated, whereby Calculate the specific gravity by measuring the weight and temperature of sulfuric acid,
The sulfuric acid concentration is measured with higher accuracy than in the first embodiment.
【００３６】なお、判定のフロー図は図２とほぼ同様で
あり、判定の結果、所定の濃度の判定値（例えば硫酸濃
度が１％以上）であった場合には、切替バルブ６３の切
替により、石膏反応槽５２へ給液するためにラインを切
替るようにすればよい。Note that the flow chart of the determination is almost the same as that of FIG. 2, and when the result of the determination is a determination value of a predetermined concentration (for example, the sulfuric acid concentration is 1% or more), the switching valve 63 is switched. The line may be switched to supply liquid to the gypsum reaction tank 52.
【００３７】また、所定の濃度の判定値（例えば硫酸濃
度が１％以下）の場合には、増湿冷却用の供給水又は触
媒水分添加用の散水として利用すると共に、硫酸濃度が
１％を超える場合には触媒水分添加用のラインのみ工水
に切り替え、硫酸を増湿冷却用にのみ利用することによ
り硫酸を濃縮するようにしてもよい。Further, in the case of a judgment value of a predetermined concentration (for example, sulfuric acid concentration is 1% or less), it is used as feed water for humidification cooling or sprinkling water for adding catalyst moisture, and the sulfuric acid concentration is 1%. If the amount exceeds the limit, the line for catalyst water addition may be switched to working water, and the sulfuric acid may be used only for humidifying and cooling to concentrate the sulfuric acid.
【００３８】以上のように、脱硫装置から排出される硫
酸濃度が所定値以下の場合の極低濃度の硫酸を再起動時
の増湿冷却水とし使用することにより、産業廃棄物とし
ての処理する必要がなくなると共に、所定値以上の場合
には、石膏反応が効率よく行うことができ、システム効
率の向上を計ることができる。As described above, when the sulfuric acid concentration discharged from the desulfurization unit is less than the predetermined value, the extremely low concentration sulfuric acid is used as the humidified cooling water at the time of restarting, so that it is treated as industrial waste. In addition to eliminating the need, when the value is not less than the predetermined value, the gypsum reaction can be efficiently carried out, and the system efficiency can be improved.
【００３９】[0039]
【発明の効果】以上の説明したように、本発明によれ
ば、脱硫システムにおいて連続的に硫酸を計測できる硫
酸計測装置を設け、該硫酸濃度の連続的な計測により、
硫酸濃度が薄い場合には、廃棄物として処理する必要が
なくなる。また、硫酸濃度が所定値以上の場合には、硫
酸濃縮槽へ供給することで所望濃度の硫酸を効率的に製
造することができる。また、所定値以上の濃度の硫酸を
供給して石灰スラリーと反応させることで、良好な石膏
を得ることが可能となる。As described above, according to the present invention, a sulfuric acid measuring device capable of continuously measuring sulfuric acid in a desulfurization system is provided, and by continuously measuring the sulfuric acid concentration,
When the sulfuric acid concentration is low, it is not necessary to treat it as waste. When the sulfuric acid concentration is equal to or higher than a predetermined value, the sulfuric acid having a desired concentration can be efficiently produced by supplying the sulfuric acid to the sulfuric acid concentration tank. Further, it is possible to obtain good gypsum by supplying sulfuric acid having a concentration of a predetermined value or more and reacting it with the lime slurry.
【図１】本実施の形態にかかる排煙処理装置を備えた排
ガス処理システム（硫酸製造）の概略図である。FIG. 1 is a schematic diagram of an exhaust gas treatment system (sulfuric acid production) including a flue gas treatment apparatus according to the present embodiment.
【図２】硫酸濃度計測のフロー図である。FIG. 2 is a flow chart of sulfuric acid concentration measurement.
【図３】本実施の形態にかかる排煙処理装置を備えた排
ガス処理システム（石膏製造）の概略図である。FIG. 3 is a schematic diagram of an exhaust gas treatment system (gypsum production) including the smoke emission treatment device according to the present embodiment.
１ ボイラ １００ 排ガス ２ 除塵機 ３ 押込みファン ４ 脱硫塔 ５ 導入口 ６ 触媒層 ７ 散水ノズル １０ 排出ポンプ １１ 硫酸タンク １２ 排出口 １３ 煙突 １６ 増湿冷却装置 １９ ミストエリミネータ ５０ 硫酸濃縮槽 ５１ 石灰スラリー ５２ 石膏反応槽 ５３ 沈降槽（シックナー） ５４ 石膏スラリー ５５ 石膏 ５６ 脱水器 ５７ 排水（濾液） ６２ 硫酸濃度計 ６３ 切替バルブ ６４ 制御手段 ６５ 測定容器 ６６ 硫酸流入ライン ６７ 硫酸排出ライン ６８ 秤 1 boiler 100 exhaust gas 2 dust remover 3 push fan 4 Desulfurization tower 5 entrance 6 Catalyst layer 7 watering nozzle 10 discharge pump 11 Sulfuric acid tank 12 outlet 13 chimney 16 Humidification cooling device 19 Mist Eliminator 50 sulfuric acid concentration tank 51 lime slurry 52 Gypsum reaction tank 53 Settling tank (thickener) 54 gypsum slurry 55 plaster 56 dehydrator 57 Wastewater (filtrate) 62 Sulfuric acid concentration meter 63 switching valve 64 control means 65 Measuring container 66 Sulfuric acid inflow line 67 Sulfuric acid discharge line 68 Scale
───────────────────────────────────────────────────── フロントページの続き (72)発明者 安武 昭典 長崎県長崎市深堀町五丁目717番１号 三 菱重工業株式会社長崎研究所内 Ｆターム(参考） 4D002 AA02 AC01 AC04 BA01 BA04 DA05 DA12 DA35 DA44 EA11 FA03 GA03 GB08 4D048 AA02 AB01 AC08 BA05X BB08 CA03 CD03 4G076 AA14 AB02 AB26 BA25 BB02 ─────────────────────────────────────────────────── ─── Continued front page (72) Inventor Akinori Yasutake 3-5-1, 717-1, Fukahori-cho, Nagasaki-shi, Nagasaki Hishi Heavy Industries Ltd. Nagasaki Research Center F-term (reference) 4D002 AA02 AC01 AC04 BA01 BA04 DA05 DA12 DA35 DA44 EA11 FA03 GA03 GB08 4D048 AA02 AB01 AC08 BA05X BB08 CA03 CD03 4G076 AA14 AB02 AB26 BA25 BB02
Claims (10)
装置塔内に設けられ、活性炭素繊維層で形成される触媒
層と、上記装置塔内に設けられ、上記触媒層に硫酸生成
用の添加水を供給する水供給手段と、上記装置塔外部又
は内部で排ガスを冷却すると共に増湿する増湿冷却手段
とからなる排煙脱硫装置と、 該排煙脱硫装置からの希硫酸と石灰スラリーとを反応さ
せ、石膏スラリーを得る石膏反応槽と、 該石膏反応槽により得られた石膏スラリーから水分を分
離して石膏を得る脱水器とを備えた排煙脱硫システムで
あって、 上記排煙脱硫装置から排出される硫酸の濃度を計測する
硫酸濃度計と、硫酸濃度計の判定結果により硫酸排出ラ
インを切替える流路切替手段とを備えたことを特徴とす
る排煙脱硫システム。1. A catalyst layer provided in an apparatus tower through which exhaust gas containing sulfur oxide flows and formed of an activated carbon fiber layer, and a catalyst layer provided in the apparatus tower for producing sulfuric acid in the catalyst layer. Flue gas desulfurization apparatus comprising water supply means for supplying additive water and humidification / cooling means for cooling and increasing the humidity of exhaust gas outside or inside the apparatus tower, and dilute sulfuric acid and lime slurry from the flue gas desulfurization apparatus A flue gas desulfurization system comprising: a gypsum reaction tank for reacting with gypsum slurry to obtain gypsum slurry; and a dehydrator for separating gypsum slurry from the gypsum slurry obtained by the gypsum reaction tank to obtain gypsum. A flue gas desulfurization system comprising a sulfuric acid concentration meter for measuring the concentration of sulfuric acid discharged from a desulfurization device, and a flow path switching means for switching a sulfuric acid discharge line according to the determination result of the sulfuric acid concentration meter.
装置塔内に設けられ、活性炭素繊維層で形成される触媒
層と、上記装置塔内に設けられ、上記触媒層に硫酸生成
用の添加水を供給する水供給手段と、上記装置塔外部又
は内部で排ガスを冷却すると共に増湿する増湿冷却手段
とからなる排煙脱硫装置と、 上記脱硫装置で得られた希硫酸を濃縮する濃縮槽とを備
えた排煙脱硫システムであって、 上記排煙脱硫装置から排出される硫酸の濃度を計測する
硫酸濃度計と、硫酸濃度計の判定結果により硫酸排出ラ
インを切替える切替手段とを備えたことを特徴とする排
煙脱硫システム。2. A catalyst layer which is provided in an apparatus tower through which exhaust gas containing sulfur oxide flows and is formed of an activated carbon fiber layer, and a catalyst layer which is provided in the apparatus tower and is used for producing sulfuric acid in the catalyst layer. A flue gas desulfurization device comprising a water supply means for supplying added water and a humidification / cooling means for cooling and humidifying exhaust gas outside or inside the apparatus tower, and dilute sulfuric acid obtained by the desulfurization apparatus is concentrated. A flue gas desulfurization system having a concentrating tank, comprising a sulfuric acid concentration meter for measuring the concentration of sulfuric acid discharged from the flue gas desulfurization device, and a switching means for switching the sulfuric acid discharge line according to the determination result of the sulfuric acid concentration meter. A flue gas desulfurization system characterized by being equipped.
酸の送液を石膏反応槽とすると共に、判定値未満の場合
には、硫酸の送液を増湿冷却装置又は水供給手段のいず
れか一方又は両方とすることを特徴とする排煙脱硫シス
テム。3. The method according to claim 1, wherein the sulfuric acid discharge line is switched to a gypsum reaction tank when the judgment value is equal to or higher than the judgment value, and when the judgment value is lower than the judgment value. A flue gas desulfurization system characterized in that a liquid is used as either or both of a humidification cooling device and a water supply means.
備えた所定容積の計測槽と、該計測槽の重量を測定する
秤とを具備してなり、硫酸を連続的に給液しつつ濃度を
計測することを特徴とする排煙脱硫システム。4. The measuring tank according to any one of claims 1 to 3, wherein the sulfuric acid concentration meter has a sulfuric acid inflow line and a sulfuric acid discharging line and has a predetermined volume, and a scale for measuring the weight of the measuring tank. A flue gas desulfurization system that is equipped with and continuously measures the concentration of sulfuric acid while measuring the concentration.
る排煙脱硫システム。5. The flue gas desulfurization system according to claim 1, wherein the sulfuric acid concentration of the determination value is 1% or more.
と該排ガスの排出口を上記装置塔の上部及び下部に有す
ると共に、該塔内に設けられた触媒槽層の上方に硫酸生
成用の水の供給器を備えたことを特徴とする排煙脱硫シ
ステム。6. The flue gas desulfurization device according to claim 1 or 2, wherein the flue gas desulfurization device has an inlet for exhaust gas containing sulfur oxides and an outlet for the exhaust gas at an upper part and a lower part of the device tower, and A flue gas desulfurization system characterized by comprising a water supply device for producing sulfuric acid above the provided catalyst tank layer.
焼却炉から排出されるガスであり、排ガス中の煤塵を除
去する煤塵除去手段を備えてなることを特徴とする排煙
脱硫システム。7. The method according to claim 1 or 2, wherein the exhaust gas is a gas discharged from a boiler, a gas turbine, an engine and various incinerators, and a soot removing means for removing soot dust in the exhaust gas is provided. Flue gas desulfurization system.
装置塔内に設けられ、活性炭素繊維層で形成される触媒
層と、 上記装置塔内に設けられ、上記触媒層に硫酸生成用の水
を供給する水供給手段とからなる排煙脱硫装置からの硫
酸の濃度を計測し、 硫酸濃度が１％以下の場合には、増湿冷却用の供給水又
は触媒水分添加用の散水として利用すると共に、硫酸濃
度が１％を超える場合には、石灰スラリーと反応して石
膏を得ることを特徴とする排煙脱硫システムの運転方
法。8. A catalyst layer provided in an apparatus tower through which exhaust gas containing sulfur oxide flows and formed of an activated carbon fiber layer; and a catalyst layer provided in the apparatus tower for producing sulfuric acid in the catalyst layer. Measure the concentration of sulfuric acid from the flue gas desulfurization unit consisting of water supply means to supply water. If the sulfuric acid concentration is 1% or less, use it as supply water for humidification cooling or sprinkling water for adding catalyst moisture. In addition, when the sulfuric acid concentration exceeds 1%, a method of operating a flue gas desulfurization system, characterized by reacting with lime slurry to obtain gypsum.
装置塔内に設けられ、活性炭素繊維層で形成される触媒
層と、 上記装置塔内に設けられ、上記触媒層に硫酸生成用の水
を供給する水供給手段とからなる排煙脱硫装置からの硫
酸の濃度を計測し、 硫酸濃度が１％以下の場合には、増湿冷却用の供給水又
は触媒水分添加用の散水として利用すると共に、硫酸濃
度が１％を超える場合には硫酸を濃縮することを特徴と
する排煙脱硫システムの運転方法。9. A catalyst layer, which is provided in an apparatus tower through which exhaust gas containing sulfur oxides flows, and which is formed of an activated carbon fiber layer, and a catalyst layer, which is provided in the apparatus tower, for producing sulfuric acid. Measure the concentration of sulfuric acid from the flue gas desulfurization unit consisting of water supply means to supply water. If the sulfuric acid concentration is 1% or less, use it as supply water for humidification cooling or sprinkling water for adding catalyst moisture. In addition, the method for operating a flue gas desulfurization system is characterized in that sulfuric acid is concentrated when the sulfuric acid concentration exceeds 1%.
る装置塔内に設けられ、活性炭素繊維層で形成される触
媒層と、 上記装置塔内に設けられ、上記触媒層に硫酸生成用の水
を供給する水供給手段とからなる排煙脱硫装置からの硫
酸の濃度を計測し、 硫酸濃度が１％以下の場合には、増湿冷却用の供給水又
は触媒水分添加用の散水として利用すると共に、硫酸濃
度が１％を超える場合には触媒水分添加用のラインのみ
工水に切り替え、硫酸を増湿冷却用にのみ利用すること
により硫酸を濃縮することを特徴とする排煙脱硫システ
ムの運転方法。10. A catalyst layer provided in an apparatus tower through which exhaust gas containing sulfur oxide flows and formed of an activated carbon fiber layer; and a catalyst layer provided in the apparatus tower for producing sulfuric acid in the catalyst layer. Measure the concentration of sulfuric acid from the flue gas desulfurization unit consisting of water supply means to supply water. If the sulfuric acid concentration is 1% or less, use it as supply water for humidification cooling or sprinkling water for adding catalyst moisture. In addition, when the sulfuric acid concentration exceeds 1%, the flue gas desulfurization system is characterized in that only the line for adding catalyst moisture is switched to working water and the sulfuric acid is used only for humidification and cooling to concentrate the sulfuric acid. Driving method.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2001349808A JP3924157B2 (en) | 2001-11-15 | 2001-11-15 | Flue gas desulfurization system and method |
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| Publication Number | Publication Date |
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| JP2003144849A true JP2003144849A (en) | 2003-05-20 |
| JP3924157B2 JP3924157B2 (en) | 2007-06-06 |
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| JP2001349808A Expired - Fee Related JP3924157B2 (en) | 2001-11-15 | 2001-11-15 | Flue gas desulfurization system and method |
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| Country | Link |
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| JP (1) | JP3924157B2 (en) |
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| CN102836626A (en) * | 2011-06-26 | 2012-12-26 | 吴火成 | Multifunctional chimney tower |
| CN103292337A (en) * | 2013-07-02 | 2013-09-11 | 湖南天通无腐烟囱工程有限公司 | Desulfurizing and smoke removal chimney |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102836626A (en) * | 2011-06-26 | 2012-12-26 | 吴火成 | Multifunctional chimney tower |
| CN103292337A (en) * | 2013-07-02 | 2013-09-11 | 湖南天通无腐烟囱工程有限公司 | Desulfurizing and smoke removal chimney |
| CN103611406A (en) * | 2013-12-10 | 2014-03-05 | 太原理工大学 | Magnetic separation device and method for sulfur dioxide in smoke |
| CN104069728A (en) * | 2014-07-04 | 2014-10-01 | 际华三五三九制鞋有限公司 | High-pressure sulfide exhaust gas treatment device |
| CN105664693A (en) * | 2016-01-15 | 2016-06-15 | 赤峰富邦铜业有限责任公司 | Sulfuric acid tail gas desulphurization apparatus by oxidation process and usage method thereof |
| WO2022014165A1 (en) * | 2020-07-15 | 2022-01-20 | 富士電機株式会社 | Exhaust gas treatment device |
| CN114867544A (en) * | 2020-07-15 | 2022-08-05 | 富士电机株式会社 | Exhaust gas treatment device |
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