JP5299600B2 - Exhaust gas treatment method and exhaust gas treatment apparatus - Google Patents

Exhaust gas treatment method and exhaust gas treatment apparatus Download PDF

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JP5299600B2
JP5299600B2 JP2007211777A JP2007211777A JP5299600B2 JP 5299600 B2 JP5299600 B2 JP 5299600B2 JP 2007211777 A JP2007211777 A JP 2007211777A JP 2007211777 A JP2007211777 A JP 2007211777A JP 5299600 B2 JP5299600 B2 JP 5299600B2
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exhaust gas
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俊一朗 上野
博之 鎌田
俊之 内藤
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<P>PROBLEM TO BE SOLVED: To provide an exhaust gas treating method and a treatment apparatus with which mercury can be highly efficiently removed regardless of the kinds of coal or properties of exhaust gas discharged from a combustion apparatus when burning the coal in the combustion apparatus like a boiler, and a further reduced cost can be achieved. <P>SOLUTION: In the exhaust gas treating method for removing mercury contained in exhaust gas discharged from a coal-burning boiler B when burning fossil fuel like coal in the coal-burning boiler B, the fossil fuel carried from a coal storage yard 20 is fed to the combustion apparatus for combustion, and absorbing liquid is brought into contact with the exhaust gas discharged from the coal-burning boiler B to perform removal process like desulfurization, in a wet desulfurization part 7 disposed in a flue R from the coal-burning boiler B. The chlorine-containing absorbing liquid being the used absorbing liquid from the wet desulfurization part 7, is fed to at least one of the coal storage yard 20, coal-burning boiler B, and the flue R from the coal-burning boiler B to the wet desulfurization part 7. <P>COPYRIGHT: (C)2009,JPO&amp;INPIT

Description

本発明は、例えば、石炭などの化石燃料をボイラなどの燃焼装置によって燃焼させる際に、この燃焼装置から排出される排ガス中に含まれる水銀を除去するのに用いられる排ガス処理方法及び排ガス処理装置に関するものである。   The present invention relates to an exhaust gas treatment method and an exhaust gas treatment device that are used to remove mercury contained in exhaust gas discharged from a combustion device when fossil fuel such as coal is burned by a combustion device such as a boiler. It is about.

上記した化石燃料の燃焼装置、例えば、石炭焚きボイラから排出される石炭の燃焼排ガスには、石炭に起因する水銀が含まれている。この水銀は、難溶性の金属水銀Hgと、水溶性の2価水銀Hg2+(HgCl)と、燃焼灰に付着した粒子状水銀Hgとの三つの形態に分かれて排ガス中に存在する。
この水銀を排ガスから除去する排ガス処理装置としては、例えば、石炭焚きボイラから煙突に至るまでの煙道に、脱硝部、脱塵部及び湿式の脱硫部を順次配置して成るものがある。
Mercury resulting from coal is contained in the above-described fossil fuel combustion apparatus, for example, coal combustion exhaust gas discharged from a coal-fired boiler. This mercury is present in the exhaust gas in three forms: hardly soluble metallic mercury Hg 0 , water-soluble divalent mercury Hg 2+ (HgCl 2 ), and particulate mercury Hg P adhering to combustion ash. .
As an exhaust gas treatment apparatus for removing mercury from exhaust gas, for example, there is an apparatus in which a denitration part, a dust removal part, and a wet desulfurization part are sequentially arranged in a flue from a coal-fired boiler to a chimney.

排ガス中に含まれる水銀のうちの粒子状水銀Hgは、その大半がこの排ガス処理装置の電気集じん器やバグフィルタなどの脱塵部で除去され、2価水銀Hg2+は、湿式の脱硫部で高効率に除去されるが、排ガス中に含まれる金属水銀Hgは、脱塵部や脱硫部でほとんど除去されずに大部分が大気に放出されているのが現状である。
大気中に放出された金属水銀Hgは、環境中でより有害な有機水銀(メチル水銀)に変換されるので、この有機水銀が魚貝類などの食用生物に蓄積されて、これが食物連鎖を経て人体内へ入り込むことが懸念されている。
Of the mercury contained in the exhaust gas, most of the particulate mercury Hg P is removed by a dust removal part such as an electric dust collector or a bag filter of this exhaust gas treatment device, and the divalent mercury Hg 2+ is wet desulfurization. However, most of the metallic mercury Hg 0 contained in the exhaust gas is released to the atmosphere without being almost removed by the dedusting part or the desulfurization part.
Metallic mercury Hg 0 released into the atmosphere is converted into more harmful organic mercury (methylmercury) in the environment, and this organic mercury is accumulated in edible organisms such as fish and shellfish, which passes through the food chain. There is concern about entering the human body.

この現状を踏まえて、米国環境保護局では、石炭焚き火力発電所からの水銀排出量を規制することを決定していて、水銀排出量を2010年までに現行の30%削減し、さらに、2018年までに現行の70%削減することを義務付けており、これと同様に、カナダでも石炭焚き火力発電所からの水銀排出量の規制を決定している。
排ガス中に含まれる金属水銀Hgは、水銀と同じく石炭に含まれる塩素に起因する塩化水素(HCl)によって、反応式(1)に示すように、脱硝触媒や石炭灰や未燃焼分炭素の表面上で酸化される。
In light of this situation, the US Environmental Protection Agency has decided to regulate mercury emissions from coal-fired thermal power plants, reducing mercury emissions by 30% by 2010, and 2018 In the same way, Canada has decided to regulate mercury emissions from coal-fired thermal power plants.
Metallic mercury Hg 0 contained in the exhaust gas is converted into denitration catalyst, coal ash, and unburned carbon as shown in the reaction formula (1) by hydrogen chloride (HCl) caused by chlorine contained in coal as well as mercury. Oxidized on the surface.

Hg+2HCl+1/2O→ HgCl+HO 反応式(1)
但し、2価水銀Hg2+はHgClである。
脱硝触媒上での水銀酸化効率は、HCl濃度が高い程高くなる。つまり、塩化水素濃度が高い程HgClの生成割合が増加することとなり、その結果、脱塵部や脱硫部で捕集される水銀の割合も増加する。
Hg 0 + 2HCl + 1 / 2O 2 → HgCl 2 + H 2 O Reaction formula (1)
However, divalent mercury Hg 2+ is HgCl 2 .
The mercury oxidation efficiency on the denitration catalyst increases as the HCl concentration increases. That is, the higher the hydrogen chloride concentration, the higher the generation ratio of HgCl 2 , and as a result, the ratio of mercury collected in the dedusting section and desulfurization section also increases.

従来において、燃焼装置から排出される排ガス中の水銀を除去する技術として、煤塵を除去する電気集じん器やバグフィルタなどの脱塵部の上流に、活性炭などの水銀吸着剤を吹き込み、この吸着剤表面に水銀を吸着させて除去する方法が提案されている(例えば、特許文献1参照)。
しかし、この吸着剤を用いた除去技術では、吸着剤を常時吹き込む必要があるため、ランニングコストが高くつくうえ、排ガス中のHCl濃度などのガス性状により効率が変化するといった欠点がある。
Conventionally, as a technology for removing mercury in exhaust gas discharged from combustion equipment, mercury adsorbents such as activated carbon are blown upstream of dust removal parts such as electric dust collectors and bag filters that remove dust. There has been proposed a method for removing mercury by adsorbing mercury on the surface of the agent (see, for example, Patent Document 1).
However, this removal technique using an adsorbent has the disadvantages that the adsorbent needs to be constantly blown, so that the running cost is high and the efficiency varies depending on the gas properties such as HCl concentration in the exhaust gas.

この排ガス中のHCl濃度に関して言えば、元来、石炭中に含まれる塩素の量が、数ppmから数100ppmと少ないのに加えて、石炭の種類によって含有量に大きなバラツキがあり、これを燃焼排ガス中のHCl濃度に換算すると、1ppm未満から数10ppmとなってしまい、このように排ガス中のHCl濃度が低い場合には、排ガスの性状にもよるが、脱硝触媒や未燃分炭素や灰上での水銀酸化効率が低下し、これに伴って脱塵部及び脱硫部での水銀捕集効率も低下する。   In terms of the concentration of HCl in the exhaust gas, the amount of chlorine contained in the coal is originally small, from several ppm to several hundred ppm, and the content varies greatly depending on the type of coal. When converted to the HCl concentration in the exhaust gas, the concentration is less than 1 ppm to several tens of ppm. If the HCl concentration in the exhaust gas is low, the denitration catalyst, unburned carbon and ash, depending on the properties of the exhaust gas, are used. The mercury oxidation efficiency in the above is lowered, and accordingly, the mercury collecting efficiency in the dedusting part and the desulfurization part is also lowered.

これに対応するべく、石炭焚きボイラからの煙道中にハロゲンを含む物質を注入する方法(例えば、特許文献2参照)や、塩素化合物を石炭とともに燃焼装置に供給して燃焼させた後、電気集じん器などの脱塵部の前で排ガス温度を150℃以下に冷却して、脱塵部において水銀の除去を行う方法(例えば、特許文献3参照)が提案されている。
米国特許第6521021号 特開平10-230137号公報 特開2000-325747号公報
In order to cope with this, a method of injecting a halogen-containing substance into a flue from a coal-fired boiler (see, for example, Patent Document 2), or supplying a chlorine compound together with coal to a combustion apparatus for combustion, A method has been proposed in which the exhaust gas temperature is cooled to 150 ° C. or lower in front of a dust removing unit such as a duster and mercury is removed in the dust removing unit (see, for example, Patent Document 3).
U.S. Patent No. 6521021 Japanese Patent Laid-Open No. 10-230137 JP 2000-325747 A

ところが、上記した煙道中にハロゲンを含む物質を注入して水銀を除去する方法や、塩素化合物を石炭とともに燃焼装置に供給して燃焼させて脱塵部において水銀の除去を行う方法では、脱硝触媒や未燃分炭素や灰上での水銀酸化効率を上げるために、排ガス中の塩化水素濃度を高くする必要がある。
つまり、塩素化合物のような薬剤類を新たに添加する必要があり、石炭を燃焼させる場合には、膨大な量を燃焼させるので、それに見合うだけの大量の塩素が必要になって、その分だけコストの上昇を招いてしまうという問題があり、この問題を解決することが従来の課題となっている。
However, in the method of removing mercury by injecting a halogen-containing substance into the flue as described above, or the method of supplying chlorine to a combustion device together with coal and burning it to remove mercury in the dedusting part, a denitration catalyst In order to increase mercury oxidation efficiency on unburned carbon and ash, it is necessary to increase the hydrogen chloride concentration in the exhaust gas.
In other words, chemicals such as chlorine compounds need to be newly added, and when burning coal, a huge amount of fuel is burned, so a large amount of chlorine is needed to meet that, and only that much. There is a problem of increasing the cost, and it has been a conventional problem to solve this problem.

本発明は、上記した課題を解決するためになされたもので、化石燃料、例えば、石炭をボイラなどの燃焼装置によって燃焼させる際に、石炭の種類や燃焼装置から排出される排ガスの性状にかかわりなく、水銀を高い効率で除去することができ、加えて、より一層の低コスト化を実現することが可能である排ガス処理方法及び排ガス処理装置を提供することを目的としている。   The present invention has been made to solve the above-described problems, and relates to the type of coal and the properties of exhaust gas discharged from the combustion device when fossil fuel, for example, coal, is burned by a combustion device such as a boiler. In addition, an object of the present invention is to provide an exhaust gas treatment method and an exhaust gas treatment apparatus that can remove mercury with high efficiency and can realize further cost reduction.

本発明の請求項1に係る発明は、化石燃料を燃焼装置で燃焼させる際に当該燃焼装置から排出される排ガス中に含まれる水銀を除去する排ガス処理方法であって、貯蔵場から運ばれた前記化石燃料を前記燃焼装置に供給して燃焼させ、前記燃焼装置からの煙道に配置された脱硝部において、金属水銀と前記排ガス中に含まれる塩化水素とを反応させて水溶性の2価水銀に酸化させ、前記煙道の前記脱硝部の下流に配置された脱塵部において、前記脱硝部からの2価水銀を煤塵とともに捕集し、前記煙道の前記脱塵部の下流に配置された湿式除去部において、前記脱塵部を通過した2価水銀を液相で吸収して捕集すると共に、前記燃焼装置から排出された排ガスに吸収液を接触させて脱硫を行って、この湿式除去部からの使用済吸収液である塩素含有吸収液の水分を減らして塩素濃度を高めた後に、この塩素濃度を高めた塩素含有吸収液を前記貯蔵場、前記燃焼装置及びこの燃焼装置から湿式除去部に至る煙道のうちの少なくとも一箇所に供給して、前記燃焼装置から排出される排ガス中に含まれる塩化水素濃度を高くし、前記燃焼装置から前記湿式除去部に至る煙道に供給される前記塩素濃度を高めた塩素含有吸収液は、記脱硝部の前記燃焼装置側煙道に供給される構成としたことを特徴としており、この排ガス処理方法の構成を前述した従来の課題を解決するための手段としている。 The invention according to claim 1 of the present invention is an exhaust gas treatment method for removing mercury contained in exhaust gas discharged from a combustion apparatus when fossil fuel is burned by the combustion apparatus, and is carried from a storage place. The fossil fuel is supplied to the combustion device and combusted, and in a denitration section disposed in the flue from the combustion device, metal mercury reacts with hydrogen chloride contained in the exhaust gas to produce a water-soluble divalent. Oxidized into mercury and collected at the dedusting part disposed downstream of the denitration part of the flue, collecting divalent mercury from the denitration part together with soot, and disposed downstream of the dedusting part of the flue in wet removal unit that is, the while absorbing to collect at the dust removal unit divalent mercury liquid phase having passed through the, row desulfurization is brought into contact with absorption liquid in the discharged flue gas from the combustion device, Salt that is a used absorbent from this wet removal section After reducing the water content of the containing absorbent and increasing the chlorine concentration, the chlorine containing absorbent containing the increased chlorine concentration is supplied to at least one of the storage, the combustion device, and the flue from the combustion device to the wet removal section. Chlorine-containing absorption that is supplied to a location, increases the concentration of hydrogen chloride contained in the exhaust gas discharged from the combustion device, and increases the concentration of chlorine supplied to the flue from the combustion device to the wet removal section liquid is characterized in that the supplied Ru configured to the combustion apparatus flue before Kida'硝部, and a means for solving the conventional problems described above the configuration of the exhaust gas treatment method.

本発明の請求項2に係る排ガス処理方法において、前記塩素濃度を高めた塩素含有吸収液を化石燃料としての石炭の貯蔵場である貯炭場に吹きかけて供給する構成としている。
本発明の請求項3に係る排ガス処理方法において、前記塩素濃度を高めた塩素含有吸収液を前記燃焼装置に用いる二次燃焼用空気に混入させて当該燃焼装置に供給する構成としている。
In the exhaust gas treatment method according to claim 2 of the present invention, the chlorine-containing absorbing liquid having an increased chlorine concentration is supplied by being sprayed to a coal storage that is a coal storage for fossil fuel.
In the exhaust gas treatment method according to claim 3 of the present invention, the chlorine-containing absorbing liquid having an increased chlorine concentration is mixed with the secondary combustion air used in the combustion device and supplied to the combustion device.

一方、本発明の請求項4に係る発明は、化石燃料を燃焼装置で燃焼させる際に当該燃焼装置から排出される排ガス中に含まれる水銀を除去する排ガス処理装置であって、前記燃焼装置からの煙道に配置されて金属水銀と前記排ガス中に含まれる塩化水素とを反応させて水溶性の2価水銀に酸化させる脱硝部と、前記燃焼装置からの煙道に配置されて前記脱硝部からの2価水銀を煤塵とともに捕集する脱塵部と、前記燃焼装置からの煙道に配置されて前記燃焼装置から排出された排ガスに吸収液を接触させて脱硫を行うと共に、前記脱塵部を通過した2価水銀を液相で吸収して捕集する湿式除去部と、前記燃焼装置から排出される排ガス中に含まれる塩化水素濃度を高くするべく、前記湿式除去部から使用済吸収液である塩素含有吸収液を前記化石燃料の貯蔵場、前記燃焼装置及びこの燃焼装置から湿式除去部に至る煙道のうちの少なくとも一箇所に供給する塩素含有吸収液供給部と、前記貯蔵場、前記燃焼装置及びこの燃焼装置から湿式除去部に至る煙道のうちの少なくとも一箇所に供給する前記塩素含有吸収液の水分を減らして塩素濃度を高める吸収液濃縮部を備え、前記塩素含有吸収液供給部は、前記塩素含有吸収液を前記燃焼装置と前記湿式除去部との間に位置する前記脱硝部の前記燃焼装置側煙道に供給する煙道送給管を具備している構成としている。 On the other hand, the invention according to claim 4 of the present invention is an exhaust gas treatment device that removes mercury contained in exhaust gas discharged from the combustion device when fossil fuel is combusted by the combustion device. A denitration unit disposed in the flue and reacting metal mercury with hydrogen chloride contained in the exhaust gas to oxidize to water-soluble divalent mercury, and a denitration unit disposed in the flue from the combustion device A dedusting part that collects divalent mercury from the dust together with soot, and desulfurization by contacting the absorbing solution with the exhaust gas disposed in the flue from the combustion device and exhausted from the combustion device, and the dust removal Wet removal part that absorbs and collects divalent mercury that has passed through the part in the liquid phase, and used absorption part from the wet removal part to increase the concentration of hydrogen chloride contained in the exhaust gas discharged from the combustion device The chlorine-containing absorbent that is liquid From a storage location for stone fuel, the combustion device and a chlorine-containing absorbent supply unit for supplying at least one of the flue leading from the combustion device to the wet removal unit, the storage site, the combustion device and the combustion device An absorption liquid concentrating section for reducing the water content of the chlorine-containing absorption liquid supplied to at least one of the flues leading to the wet removal section to increase the chlorine concentration, and the chlorine-containing absorption liquid supply section includes the chlorine-containing absorption It has a configuration which comprises a sheet tube feeding flue supplied to the combustion apparatus flue of the denitration unit located between the liquid and the combustion device and the wet removal unit.

本発明の請求項に係る発明において、前記塩素含有吸収液供給部は、前記塩素含有吸収液を化石燃料としての石炭の貯蔵場である貯炭場に吹きかけて供給する貯炭場送給管を具備している構成としている。
本発明の請求項に係る発明において、前記塩素含有吸収液供給部は、前記燃焼装置に二次燃焼用空気を導入する二次燃焼用空気導入路に連通する送給管を具備している構成としている。
In the invention which concerns on Claim 5 of this invention, the said chlorine containing absorption liquid supply part is equipped with the coal storage feed pipe which sprays and supplies the said chlorine containing absorption liquid to the coal storage which is a storage of coal as a fossil fuel. It has a configuration.
In the invention according to claim 6 of the present invention, the chlorine-containing absorbent supply section includes a feed pipe communicating with a secondary combustion air introduction path for introducing secondary combustion air into the combustion device. It is configured.

本発明の排ガス処理方法及び排ガス処理装置において、燃焼装置からの煙道に配置した脱硝部では、その内部の脱硝触媒上や、煙道中に存在する未燃炭素分や灰分の表面などで、HgとHClとを反応させてHgClに酸化させる。 In the exhaust gas treatment method and exhaust gas treatment apparatus of the present invention, in the denitration part disposed in the flue from the combustion device, Hg on the denitration catalyst inside the surface, the surface of unburned carbon and ash present in the flue, etc. 0 and allowed to react with HCl to oxidize to HgCl 2 in.

本発明の請求項1に係る排ガス処理方法及び請求項に係る排ガス処理装置では、上記した構成としているので、燃焼装置から排出される排ガス中の塩化水素の濃度が高くなることで、燃焼装置からの煙道や、例えば、この煙道に配置される脱硝部における水銀酸化効率が上昇して水溶性の2価水銀の生成割合が増加することから、湿式除去部である脱硫部や、通常煙道に配置される脱塵部における水銀捕集量が増加する。 Since the exhaust gas treatment method according to claim 1 and the exhaust gas treatment apparatus according to claim 4 of the present invention have the above-described configuration, the concentration of hydrogen chloride in the exhaust gas discharged from the combustion device increases, so that the combustion device From the flue from the air, for example, the mercury oxidation efficiency in the denitration part arranged in this flue is increased and the production rate of water-soluble divalent mercury is increased. Increases the amount of mercury collected in the dedusting section located in the flue.

この水銀除去には、吸着剤を用いていないので、その分だけランニングコストを少なく抑え得るうえ、排ガス中のHCl濃度などのガス性状によって水銀捕集効率が低下しない。
つまり、石炭の種類や燃焼装置から排出される排ガスの性状にかかわりなく、水銀を高効率且つ低コストで除去することが可能であり、加えて、前記貯蔵場、前記燃焼装置及びこの燃焼装置から湿式除去部に至る煙道のうちの少なくとも一箇所に供給する塩素含有吸収液は、湿式除去部で排ガスに吸収液を接触させて脱硫などの除去を行ってできた使用済吸収液であることから、塩素化合物などの添加物を別途揃える必要がない分だけ、より一層の低コスト化を実現することが可能である。
Since no adsorbent is used for this mercury removal, the running cost can be reduced correspondingly, and the mercury collection efficiency does not decrease due to gas properties such as HCl concentration in the exhaust gas.
In other words, it is possible to remove mercury with high efficiency and low cost regardless of the type of coal and the nature of the exhaust gas discharged from the combustion device, and in addition, from the storage, the combustion device and the combustion device. The chlorine-containing absorbent supplied to at least one of the flues leading to the wet removal section is a used absorbent that has been removed by bringing the absorbent into contact with the exhaust gas in the wet removal section and removing it such as desulfurization. Therefore, it is possible to further reduce the cost because it is not necessary to separately prepare additives such as chlorine compounds.

また、本発明の請求項に係る排ガス処理方法及び請求項に係る排ガス処理装置では、塩素濃度が高い塩素含有吸収液を前記貯蔵場、前記燃焼装置及びこの燃焼装置から湿式除去部に至る煙道のうちの少なくとも一箇所に供給し得るので、蒸発潜熱分の熱量損失を少なく抑えることができる。
さらに、本発明の請求項に係る排ガス処理方法及び請求項に係る排ガス処理装置では、とくに、脱硝触部における水銀酸化効率が上昇するので、水溶性の2価水銀の生成割合をより一層増加させることが可能である。
Further, in the air pollution control apparatus according to the exhaust gas processing method and claim 4 according to claim 1 of the present invention leads to wet removal portion chlorine concentration is high chlorine content absorbing solution the storage field, from the combustion apparatus and the combustion device Since it can supply to at least one place of a flue, the calorie | heat amount loss for a vaporization latent heat can be suppressed small.
Furthermore, in the air pollution control apparatus according to the exhaust gas processing method and claim 4 according to claim 1 of the present invention, in particular, because mercury oxidation efficiency increases in denitration catalyst unit, even more the production ratio of divalent mercury soluble It is possible to increase.

さらにまた、本発明の請求項に係る排ガス処理方法及び請求項に係る排ガス処理装置では、石炭の貯蔵場である貯炭場に塩素含有吸収液を吹きかけるようにしているので、石炭の自然発火を防ぐことができる。
さらにまた、本発明の請求項に係る排ガス処理方法及び請求項に係る排ガス処理装置では、二次燃焼用空気とともに塩素含有吸収液を燃焼装置に供給するようにしているので、高温下で一気に気化分解させることができ、その結果、ガス状の塩化水素を効率よく生成させることが可能である。
Furthermore, in the exhaust gas treatment method according to claim 2 of the present invention and the exhaust gas treatment apparatus according to claim 5 , since the chlorine-containing absorbent is sprayed on the coal storage that is a coal storage, Can be prevented.
Furthermore, in the exhaust gas treatment method according to claim 3 of the present invention and the exhaust gas treatment device according to claim 6 , the chlorine-containing absorbent is supplied to the combustion device together with the secondary combustion air. It can be vaporized and decomposed at once, and as a result, gaseous hydrogen chloride can be efficiently generated.

以下、本発明の実施形態を図面に基づいて説明する。
図1は、本発明の一実施形態による排ガス処理装置を示しており、この実施形態では、本発明の排ガス処理方法及び排ガス処理装置を石炭焚きボイラ(燃焼装置)から排出される排ガスの処理に適用した場合を例に挙げて説明する。
図1に示すように、この排ガス処理装置1は、石炭焚きボイラBから煙突2に至るまでの煙道Rに順次配置した脱硝部3、エアヒータ4、脱塵部5、熱交換器6、湿式除去部としての湿式脱硫部7及び熱交換器8を備えており、石炭焚きボイラBには、貯炭場20の石炭がミル21で粉砕されて供給されるようになっている。
Hereinafter, embodiments of the present invention will be described with reference to the drawings.
FIG. 1 shows an exhaust gas treatment apparatus according to an embodiment of the present invention. In this embodiment, the exhaust gas treatment method and the exhaust gas treatment apparatus of the present invention are used to treat exhaust gas discharged from a coal fired boiler (combustion device). The case where it is applied will be described as an example.
As shown in FIG. 1, the exhaust gas treatment apparatus 1 includes a denitration unit 3, an air heater 4, a dust removal unit 5, a heat exchanger 6, a wet type, which are sequentially arranged in a flue R from a coal burning boiler B to a chimney 2. A wet desulfurization unit 7 and a heat exchanger 8 as a removal unit are provided, and coal in the coal storage boiler 20 is supplied to the coal burning boiler B after being pulverized by a mill 21.

湿式脱硫部7は、脱塵部5側から流れる排ガスにスプレー7aを介して吸収液を吹き付けて、排ガス中の塩素化合物やSOを除去するようになっており、使用済みの吸収液は、ポンプ7bによって循環して利用された後、排水処理部9に送給されるようになっている。
また、この排ガス処理装置1は、貯炭場20、石炭焚きボイラB及びこの石炭焚きボイラBから湿式脱硫部7に至る煙道Rのうちの少なくとも一箇所に対して、排水処理部9を介して湿式脱硫部7の使用済みの吸収液を供給する塩素含有吸収液供給部10を備えており、これにより、石炭焚きボイラBから排出される排ガス中に含まれる塩化水素濃度を高くするようにしている。
The wet desulfurization unit 7 sprays an absorbing liquid on the exhaust gas flowing from the dedusting unit 5 side through the spray 7a to remove chlorine compounds and SO X in the exhaust gas. After being circulated and used by the pump 7b, it is fed to the waste water treatment section 9.
In addition, the exhaust gas treatment apparatus 1 is provided with a waste water treatment unit 9 for at least one of the coal storage 20, the coal fired boiler B, and the flue R extending from the coal fired boiler B to the wet desulfurization unit 7. A chlorine-containing absorbent supply unit 10 that supplies the used absorbent of the wet desulfurization unit 7 is provided, so that the concentration of hydrogen chloride contained in the exhaust gas discharged from the coal-fired boiler B is increased. Yes.

この塩素含有吸収液供給部10は、脱硝部3の石炭焚きボイラB側煙道Rに使用済みの吸収液を供給する煙道送給管11と、使用済みの吸収液を貯炭場20に吹きかけて供給する貯炭場送給管12と、石炭焚きボイラBに二次燃焼用空気を導入する二次燃焼用空気導入路Baに連通する送給管13と、石炭焚きボイラBに使用済みの吸収液を直接供給する送給管14を具備しており、これらの送給管11〜14は、適宜選択されて少なくとも一つが用いられるようになっている。   The chlorine-containing absorbing liquid supply unit 10 sprays the used absorbing liquid to the coal storage 20 and the flue delivery pipe 11 that supplies the used absorbing liquid to the coal-fired boiler B side flue R of the denitration unit 3. The coal storage boiler feed pipe 12, the feed pipe 13 communicating with the secondary combustion air introduction passage Ba for introducing the secondary combustion air into the coal fired boiler B, and the absorption used in the coal fired boiler B A feed pipe 14 for directly supplying the liquid is provided, and these feed pipes 11 to 14 are appropriately selected and at least one is used.

この塩素含有吸収液供給部10は、上記送給管11〜14のほか、脱硝部3及び湿式脱硫部7の間の煙道Rに使用済みの吸収液を供給する送給管15〜18を必要に応じて配置し得る構造をなしている。
この場合、排水処理部9の近傍に、吸収液濃縮部19を配置しており、排水処理部9を介して湿式脱硫部7から送られる使用済みの吸収液の水分を減らして塩素濃度を高めるようにしている。
The chlorine-containing absorbing liquid supply unit 10 includes feeding pipes 15 to 18 that supply used absorbing liquid to the flue R between the denitration unit 3 and the wet desulfurization unit 7 in addition to the feeding pipes 11 to 14. It has a structure that can be arranged as needed.
In this case, the absorption liquid concentration unit 19 is disposed in the vicinity of the waste water treatment unit 9, and the chlorine concentration is increased by reducing the water content of the used absorption liquid sent from the wet desulfurization unit 7 through the waste water treatment unit 9. I am doing so.

この排ガス処理装置1において、煙道Rにおける脱硝部3の上流側にアンモニアを添加して、排ガスに含まれるNOを還元して窒素と水に変換するようにしている。
また、脱硝部3内の脱硝触媒上や、脱硝部3内及び煙道R中に存在する未燃炭素分や灰分の表面などで、金属水銀HgとHClとを反応させて水溶性の2価水銀Hg2+(HgCl)に酸化させるようにしている。
In this air pollution control apparatus 1, by adding ammonia to the upstream side of the denitration unit 3 in the flue R, so that converted by reducing NO X contained in the exhaust gas to nitrogen and water.
Further, metal mercury Hg 0 reacts with HCl on the denitration catalyst in the denitration unit 3 or on the surface of the unburned carbon and ash present in the denitration unit 3 and in the flue R so that the water-soluble 2 Oxidized to valence mercury Hg 2+ (HgCl 2 ).

さらに、湿式脱硫部7において、脱塵部5を通過した2価水銀Hg2+(HgCl)を液相吸収し、汚泥中に取り込んで捕集するようにしている。
この排ガス処理装置1では、貯炭場20の石炭をミル21によって粉砕し、これを石炭焚きボイラBに供給して燃焼を開始させる。そして、石炭焚きボイラBから排出される排ガスの処理を行う場合には、まず、煙道Rにおける脱硝部3の上流側にアンモニアを添加して、排ガスに含まれるNOを還元して窒素と水に変換する。
Further, in the wet desulfurization section 7, the divalent mercury Hg 2+ (HgCl 2 ) that has passed through the dedusting section 5 is liquid-phase absorbed, and taken into sludge and collected.
In this exhaust gas treatment device 1, the coal in the coal storage yard 20 is pulverized by the mill 21, and supplied to the coal-fired boiler B to start combustion. When performing the processing of the exhaust gas discharged from a coal-fired boiler B, first, by adding ammonia to the upstream side of the denitration unit 3 in the flue R, and nitrogen by reducing NO X contained in the exhaust gas Convert to water.

上記石炭焚きボイラBから排出される排ガス中に含まれる水銀のうち、金属水銀Hgは、脱硝部3内の脱硝触媒上や、脱硝部3内及び煙道R中に存在する未燃炭素分や灰分の表面などで、HClと反応して水溶性の2価水銀Hg2+(HgCl)に変換される。
ここで、石炭焚きボイラBから排出される排ガス中に含まれる塩化水素濃度を高くするべく、塩素含有吸収液供給部10によって、湿式脱硫部7から使用済吸収液である塩素含有吸収液を送給管11〜14(必要に応じて送給管15〜18)のうちの少なくとも一つを介して貯炭場20や石炭焚きボイラBや脱硝部3に供給する。
Among the mercury contained in the exhaust gas discharged from the coal-fired boiler B, the metallic mercury Hg 0 is the unburned carbon content present on the denitration catalyst in the denitration unit 3 and in the denitration unit 3 and in the flue R. It reacts with HCl on the surface of ash or the like and is converted to water-soluble divalent mercury Hg 2+ (HgCl 2 ).
Here, in order to increase the concentration of hydrogen chloride contained in the exhaust gas discharged from the coal-fired boiler B, the chlorine-containing absorbent supply unit 10 sends a chlorine-containing absorbent that is a used absorbent from the wet desulfurization unit 7. It supplies to the coal storage 20, the coal burning boiler B, and the denitration part 3 via at least one of the supply pipes 11-14 (the supply pipes 15-18 as needed).

次いで、脱塵部5では、2価水銀Hg2+を煤塵とともに捕集し、湿式脱硫部7では、上記脱塵部5を通過した2価水銀Hg2+(HgCl)を液相で吸収して汚泥中に取り込んで捕集し、この後、水銀を含んだ汚泥を産業廃棄物として廃棄処理するようにしている。
上記したように、この実施形態の排ガス処理方法及び排ガス処理装置1では、石炭を石炭焚きボイラBによって燃焼させる際に、石炭焚きボイラBから排出される排ガス中の塩化水素の濃度が高くなることで、石炭焚きボイラBからの煙道Rに配置される脱硝部3などにおける水銀酸化効率が上昇して水溶性の2価水銀の生成割合が増加することから、石炭焚きボイラBからの煙道Rに配置される脱塵部5や湿式脱硫部7における水銀捕集量が増加する。
Next, the dedusting unit 5 collects divalent mercury Hg 2+ together with soot dust, and the wet desulfurization unit 7 absorbs the divalent mercury Hg 2+ (HgCl 2 ) that has passed through the dedusting unit 5 in the liquid phase. It is taken in and collected in sludge, and after that, the sludge containing mercury is disposed of as industrial waste.
As described above, in the exhaust gas treatment method and the exhaust gas treatment apparatus 1 of this embodiment, when coal is burned by the coal burning boiler B, the concentration of hydrogen chloride in the exhaust gas discharged from the coal burning boiler B is increased. Because the mercury oxidation efficiency in the denitration section 3 and the like arranged in the flue R from the coal-fired boiler B is increased and the production rate of water-soluble divalent mercury is increased, the flue from the coal-fired boiler B The amount of mercury collected in the dedusting unit 5 and the wet desulfurization unit 7 arranged in R increases.

そして、この水銀除去には、吸着剤を用いていないので、その分だけランニングコストを少なく抑え得るうえ、排ガス中のHCl濃度などのガス性状によって水銀捕集効率が低下しない。
つまり、石炭の種類や石炭焚きボイラBから排出される排ガスの性状にかかわりなく、水銀を高効率且つ低コストで除去することが可能であり、加えて、貯炭場20、石炭焚きボイラB及びこの石炭焚きボイラBから湿式脱硫部7に至る煙道Rのうちの少なくとも一箇所に供給する塩素含有吸収液は、湿式脱硫部7で排ガスに吸収液を接触させて脱硫などの除去を行ってできた使用済吸収液であることから、塩素化合物などの添加物を別途揃える必要がない分だけ、より一層の低コスト化を実現することが可能である。
Further, since no adsorbent is used for this mercury removal, the running cost can be reduced by that amount, and the mercury collection efficiency does not decrease due to gas properties such as HCl concentration in the exhaust gas.
That is, it is possible to remove mercury with high efficiency and low cost regardless of the type of coal and the nature of the exhaust gas discharged from the coal-fired boiler B. In addition, the coal storage 20, the coal-fired boiler B, and this The chlorine-containing absorbent supplied to at least one of the flues R from the coal-fired boiler B to the wet desulfurization section 7 is obtained by removing the desulfurization and the like by contacting the absorbent with the exhaust gas in the wet desulfurization section 7. Further, since it is a used absorbent, it is possible to realize further cost reduction because it is not necessary to separately prepare additives such as chlorine compounds.

また、上記した排ガス処理装置1では、排水処理部9の近傍に吸収液濃縮部19を配置することで、排水処理部9を介して湿式脱硫部7から送られる使用済みの吸収液の水分を減らして塩素濃度を高めるようにしているので、蒸発潜熱分の熱量損失を少なく抑えることができる。   Further, in the above-described exhaust gas treatment device 1, the absorbent concentration unit 19 is disposed in the vicinity of the waste water treatment unit 9, so that the moisture of the used absorbent sent from the wet desulfurization unit 7 through the waste water treatment unit 9 can be reduced. Since the chlorine concentration is increased by reducing the heat loss, the heat loss due to the latent heat of vaporization can be reduced.

本発明の一実施形態による排ガス処理装置を示す概略構成説明図である。BRIEF DESCRIPTION OF THE DRAWINGS It is schematic structure explanatory drawing which shows the waste gas processing apparatus by one Embodiment of this invention.

符号の説明Explanation of symbols

1 排ガス処理装置
3 脱硝部
7 湿式脱硫部(湿式除去部)
10 塩素含有吸収液供給部
11〜18 送給
19 吸収液濃縮部
20 貯炭場(貯蔵場)
B 石炭焚きボイラ(燃焼装置)
Ba 二次燃焼用空気導入路
R 煙道
1 Exhaust gas treatment device 3 Denitration unit 7 Wet desulfurization unit (wet removal unit)
10 Chlorine-containing Absorbent Supply Units 11 to 18 Feed Pipe 19 Absorbent Concentrate Unit 20 Coal Storage (Storage)
B Coal-fired boiler (combustion device)
Ba Secondary combustion air introduction path R Flue

Claims (6)

化石燃料を燃焼装置で燃焼させる際に当該燃焼装置から排出される排ガス中に含まれる水銀を除去する排ガス処理方法であって、
貯蔵場から運ばれた前記化石燃料を前記燃焼装置に供給して燃焼させ、
前記燃焼装置からの煙道に配置された脱硝部において、金属水銀と前記排ガス中に含まれる塩化水素とを反応させて水溶性の2価水銀に酸化させ、
前記煙道の前記脱硝部の下流に配置された脱塵部において、前記脱硝部からの2価水銀を煤塵とともに捕集し、
前記煙道の前記脱塵部の下流に配置された湿式除去部において、前記脱塵部を通過した2価水銀を液相で吸収して捕集すると共に、前記燃焼装置から排出された排ガスに吸収液を接触させて脱硫を行って、この湿式除去部からの使用済吸収液である塩素含有吸収液の水分を減らして塩素濃度を高めた後に、
この塩素濃度を高めた塩素含有吸収液を前記貯蔵場、前記燃焼装置及びこの燃焼装置から湿式除去部に至る煙道のうちの少なくとも一箇所に供給して、前記燃焼装置から排出される排ガス中に含まれる塩化水素濃度を高くし、
前記燃焼装置から前記湿式除去部に至る煙道に供給される前記塩素濃度を高めた塩素含有吸収液は、記脱硝部の前記燃焼装置側煙道に供給され
ことを特徴とする排ガス処理方法。
An exhaust gas treatment method for removing mercury contained in exhaust gas discharged from a combustion device when fossil fuel is burned by the combustion device,
Supplying the fossil fuel carried from the storage site to the combustion device for combustion;
In a denitration part arranged in the flue from the combustion device, metal mercury and hydrogen chloride contained in the exhaust gas are reacted to be oxidized into water-soluble divalent mercury,
In the dedusting part arranged downstream of the denitration part of the flue, divalent mercury from the denitration part is collected together with soot dust,
In the wet removal section disposed downstream of the dust removal section of the flue, the bivalent mercury that has passed through the dust removal section is absorbed and collected in the liquid phase, and the exhaust gas discharged from the combustion device is collected. the absorption liquid is brought into contact with desulfurization I row, after increasing the chlorine concentration to reduce the moisture of the chlorine-containing absorbing solution is spent absorbing solution from the wet removal unit,
In the exhaust gas discharged from the combustion device by supplying the chlorine-containing absorption liquid with an increased chlorine concentration to at least one of the storage, the combustion device, and the flue leading from the combustion device to the wet removal section Increase the concentration of hydrogen chloride contained in
Exhaust gas, wherein the chlorine-containing absorbing solution increased the concentration of chlorine supplied to the flue leading to the wet removal portion from the combustion device, that will be supplied to the combustion apparatus flue before Kida'硝部Processing method.
前記塩素濃度を高めた塩素含有吸収液を化石燃料としての石炭の貯蔵場である貯炭場に吹きかけて供給する請求項1に記載の排ガス処理方法。 The exhaust gas treatment method according to claim 1, wherein the chlorine-containing absorption liquid with an increased chlorine concentration is supplied by spraying to a coal storage, which is a coal storage for fossil fuel. 前記塩素濃度を高めた塩素含有吸収液を前記燃焼装置に用いる二次燃焼用空気に混入させて当該燃焼装置に供給する請求項1又は2に記載の排ガス処理方法。 The exhaust gas treatment method according to claim 1 or 2, wherein the chlorine-containing absorbing liquid with an increased chlorine concentration is mixed with secondary combustion air used in the combustion device and supplied to the combustion device. 化石燃料を燃焼装置で燃焼させる際に当該燃焼装置から排出される排ガス中に含まれる水銀を除去する排ガス処理装置であって、
前記燃焼装置からの煙道に配置されて金属水銀と前記排ガス中に含まれる塩化水素とを反応させて水溶性の2価水銀に酸化させる脱硝部と、
前記燃焼装置からの煙道に配置されて前記脱硝部からの2価水銀を煤塵とともに捕集する脱塵部と、
前記燃焼装置からの煙道に配置されて前記燃焼装置から排出された排ガスに吸収液を接触させて脱硫を行うと共に、前記脱塵部を通過した2価水銀を液相で吸収して捕集する湿式除去部と、
前記燃焼装置から排出される排ガス中に含まれる塩化水素濃度を高くするべく、前記湿式除去部から使用済吸収液である塩素含有吸収液を前記化石燃料の貯蔵場、前記燃焼装置及びこの燃焼装置から湿式除去部に至る煙道のうちの少なくとも一箇所に供給する塩素含有吸収液供給部と、
前記貯蔵場、前記燃焼装置及びこの燃焼装置から湿式除去部に至る煙道のうちの少なくとも一箇所に供給する前記塩素含有吸収液の水分を減らして塩素濃度を高める吸収液濃縮部を備え、
前記塩素含有吸収液供給部は、前記塩素含有吸収液を前記燃焼装置と前記湿式除去部との間に位置する前記脱硝部の前記燃焼装置側煙道に供給する煙道送給管を具備している
ことを特徴とする排ガス処理装置。
An exhaust gas treatment device for removing mercury contained in exhaust gas discharged from the combustion device when fossil fuel is burned by the combustion device,
A denitration unit that is disposed in a flue from the combustion device and reacts with metallic mercury and hydrogen chloride contained in the exhaust gas to oxidize to water-soluble divalent mercury;
A dedusting unit disposed in a flue from the combustion device and collecting divalent mercury from the denitration unit together with soot and dust;
The desulfurization is performed by contacting the absorption liquid with the exhaust gas disposed in the flue from the combustion apparatus and exhausted from the combustion apparatus , and the divalent mercury that has passed through the dedusting part is absorbed and collected in the liquid phase. A wet removal section to perform ,
In order to increase the concentration of hydrogen chloride contained in the exhaust gas discharged from the combustion device, a chlorine-containing absorption liquid, which is a used absorption liquid, is supplied from the wet removal unit to the fossil fuel storage site, the combustion device, and the combustion device. A chlorine-containing absorbent supply unit that supplies to at least one of the flues leading to the wet removal unit,
An absorption liquid concentrating section that reduces the moisture of the chlorine-containing absorption liquid supplied to at least one of the storage area, the combustion apparatus and the flue leading from the combustion apparatus to the wet removal section, and increases the chlorine concentration;
The chlorine-containing absorbing solution supply unit, the chlorine-containing absorbing solution comprising the feed flue supplied to the combustion apparatus flue feeding tube of the denitration unit located between the wet removal unit and the combustion device An exhaust gas treatment apparatus characterized by that.
前記塩素含有吸収液供給部は、前記塩素含有吸収液を化石燃料としての石炭の貯蔵場である貯炭場に吹きかけて供給する貯炭場送給管を具備している請求項4に記載の排ガス処理装置。   5. The exhaust gas treatment according to claim 4, wherein the chlorine-containing absorption liquid supply unit includes a coal storage feed pipe that supplies the chlorine-containing absorption liquid by spraying the chlorine-containing absorption liquid to a coal storage that is a storage for coal as fossil fuel. apparatus. 前記塩素含有吸収液供給部は、前記燃焼装置に二次燃焼用空気を導入する二次燃焼用空気導入路に連通する送給管を具備している請求項4又は5に記載の排ガス処理装置。   6. The exhaust gas treatment apparatus according to claim 4, wherein the chlorine-containing absorption liquid supply unit includes a feed pipe communicating with a secondary combustion air introduction path that introduces secondary combustion air into the combustion apparatus. .
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