JP2007260619A - Method and apparatus for treating exhaust gas - Google Patents

Method and apparatus for treating exhaust gas Download PDF

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JP2007260619A
JP2007260619A JP2006091867A JP2006091867A JP2007260619A JP 2007260619 A JP2007260619 A JP 2007260619A JP 2006091867 A JP2006091867 A JP 2006091867A JP 2006091867 A JP2006091867 A JP 2006091867A JP 2007260619 A JP2007260619 A JP 2007260619A
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exhaust gas
wet
electrostatic precipitator
ammonia
sulfuric acid
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JP3937356B1 (en
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Shinichi Kawabata
進一 川畑
Yoshihiko Mochizuki
美彦 望月
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Hitachi Plant Technologies Ltd
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/46—Removing components of defined structure
    • B01D53/48—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
    • 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
    • B01D53/505—Sulfur oxides by treating the gases with a solution or a suspension of an alkali or earth-alkali or ammonium compound in a spray drying process
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
    • B03C—MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
    • B03C3/00—Separating dispersed particles from gases or vapour, e.g. air, by electrostatic effect
    • B03C3/01—Pretreatment of the gases prior to electrostatic precipitation
    • B03C3/013—Conditioning by chemical additives, e.g. with SO3
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
    • B03C—MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
    • B03C3/00—Separating dispersed particles from gases or vapour, e.g. air, by electrostatic effect
    • B03C3/02—Plant or installations having external electricity supply
    • B03C3/16—Plant or installations having external electricity supply wet type
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2251/00—Reactants
    • B01D2251/20—Reductants
    • B01D2251/206—Ammonium compounds
    • B01D2251/2062—Ammonia

Abstract

<P>PROBLEM TO BE SOLVED: To perform exhaust gas treatment improved on collection efficiency for a sulfuric acid mist in a wet type electrical dust precipitator. <P>SOLUTION: The method comprises: removing oxides of sulfur by wet-desulphurizing an exhaust gas; thereafter obtaining an amount of the sulfuric acid mist in the desulphurized exhaust gas; mixing with an ammonia gas having a concentration of not greater than the ratio of one equivalent to the sulfuric acid mist; and passing through the wet electrical dust precipitator to remove the sulfuric acid mist. The method can be actualized by providing an apparatus for treating the exhaust gas having the wet electrical dust precipitator for removing the oxides of sulfur in the exhaust gas and the wet type electrical dust precipitator for removing the sulfuric acid mist with a means for supplying the ammonia gas which supplies the ammonia gas to the exhaust gas introduced into the wet type electrical dust precipitator. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

本発明は排ガス処理方法および設備に係り、特に排ガス中の硫酸ミストを湿式電気集塵装置で除去する排ガス処理方法および設備に関する。   The present invention relates to an exhaust gas treatment method and equipment, and more particularly, to an exhaust gas treatment method and equipment for removing sulfuric acid mist in exhaust gas with a wet electrostatic precipitator.

一般に、石油や重油等を燃料とするボイラからの排ガスを処理する排ガス処理設備は、ボイラの後段に乾式電気集塵装置、湿式脱硫装置、湿式電気集塵装置が順に配設されている。ボイラから排出された排ガスは、まず、乾式電気集塵装置に導入されて除塵され、次いで、湿式脱硫装置に導入される。そして、この湿式脱硫装置の内部で、消石灰や水酸化マグネシウム等のスラリーを噴霧することにより、主に排ガス中の二酸化硫黄が吸収除去される。このとき、乾式電気集塵装置で百数十度だった排ガスの温度は、約数十度まで低下する。そして、脱硫された排ガスは、湿式電気集塵装置に導入され、ミスト及び固形成分が除去された後、外部に放出される。   In general, in an exhaust gas treatment facility that treats exhaust gas from a boiler that uses petroleum, heavy oil, or the like as a fuel, a dry electrostatic precipitator, a wet desulfurizer, and a wet electrostatic precipitator are arranged in this order after the boiler. The exhaust gas discharged from the boiler is first introduced into a dry electrostatic precipitator to remove dust, and then introduced into a wet desulfurization apparatus. And by spraying slurry such as slaked lime or magnesium hydroxide inside this wet desulfurization apparatus, sulfur dioxide in the exhaust gas is mainly absorbed and removed. At this time, the temperature of the exhaust gas, which has been a hundred and ten degrees in the dry electrostatic precipitator, decreases to about several tens of degrees. The desulfurized exhaust gas is introduced into a wet electrostatic precipitator, and after mist and solid components are removed, it is discharged to the outside.

ところで、排ガス中の二酸化硫黄の一部は、酸素及び水と反応して硫酸を生成する。この硫酸は、濃度が数十ｐｐｍの場合、湿式脱硫装置の内部においてガス状から液状になり、ミストを生成する。この硫酸を含むミストは、粒径が小さいため、前記噴霧スラリーとの衝突確率が低く、湿式脱硫装置で除去することが困難である。   By the way, a part of sulfur dioxide in the exhaust gas reacts with oxygen and water to produce sulfuric acid. When the concentration of this sulfuric acid is several tens of ppm, the sulfuric acid changes from a gaseous state to a liquid state inside the wet desulfurization apparatus to generate mist. Since this mist containing sulfuric acid has a small particle size, the probability of collision with the spray slurry is low, and it is difficult to remove with a wet desulfurization apparatus.

そこで、後段の湿式電気集塵装置で、前記硫酸ミストを除去することになる。しかし、湿式電気集塵装置は、ミストの粒径が小さい場合、即ち、単位体積の排ガスに占めるミストの表面積の総和（以下、比表面積と称す）が大きい場合、空間電荷効果によって放電電流が抑制され、捕集効果が低下する。このため、荷電時間を増加させることが必要となる。しかし、荷電時間を増加させると、湿式電気集塵装置の容量増加が必要となるため、装置全体が大型化する。   Therefore, the sulfuric acid mist is removed by a wet-type electrostatic precipitator at the subsequent stage. However, the wet electrostatic precipitator suppresses the discharge current due to the space charge effect when the mist particle size is small, that is, when the total surface area of the mist in the unit volume of exhaust gas (hereinafter referred to as the specific surface area) is large. This reduces the collection effect. For this reason, it is necessary to increase the charging time. However, if the charging time is increased, the capacity of the wet electrostatic precipitator needs to be increased, so that the entire apparatus becomes larger.

このようなことから、従来は、湿式脱硫装置の入口で排ガス中に粒子を供給して、ミスト粒径を大きくする手段を講じて、後段の湿式電気集塵機での補修効率を高めるようにしていた（特許文献１）。
特開２００１−１７０５１５号 For this reason, conventionally, particles have been supplied into the exhaust gas at the inlet of the wet desulfurization apparatus, and a means for increasing the mist particle size has been taken to improve the repair efficiency of the subsequent wet electrostatic precipitator. (Patent Document 1).
JP 2001-170515 A

しかし、湿式脱硫装置では、上述のように、装置内部で、消石灰や水酸化マグネシウム等のスラリーを噴霧することにより、主に排ガス中の二酸化硫黄を吸収除去する工程であるため、排ガス温度の低下を避けることができない。このことは残留硫黄分が存在する限り、湿式脱硫装置の出口ガスには硫酸ミストが含まれてしまうことを意味している。近年、排出微粒子の規制が厳しく、環境問題にも影響するため、設備の大型化を抑制しつつ、排出微粒子を少なくすることが一層要請されている。   However, in the wet desulfurization apparatus, as described above, by spraying slurry such as slaked lime or magnesium hydroxide inside the apparatus, it is a process of mainly absorbing and removing sulfur dioxide in the exhaust gas. Cannot be avoided. This means that sulfuric acid mist is contained in the outlet gas of the wet desulfurization apparatus as long as the residual sulfur content exists. In recent years, regulations on discharged particulates have become more stringent and have an impact on environmental problems. Therefore, it has been further demanded to reduce the number of discharged particulates while suppressing an increase in the size of facilities.

本発明はこのような事情に鑑みて成されたもので、湿式電気集塵装置における硫酸ミストの捕集効率を向上させることのできる排ガス処理設備を提供することを目的とする。   The present invention has been made in view of such circumstances, and an object of the present invention is to provide an exhaust gas treatment facility capable of improving the collection efficiency of sulfuric acid mist in a wet electrostatic precipitator.

本発明は、湿式脱硫装置における温度低下により排ガス中に含まれる硫酸の凝縮によって生じるミストとアンモニアガスとを等量混合させた状態を作り出し、これを滞湿式電気集塵装置に導入までの滞留時間を一定以上確保させれば無害な硫酸アンモニウム（酸性硫安）を生成しつつ、リークアンモニアガスを低減するとができるとの知見を得てなされたものである。   The present invention creates a state in which an equal amount of mist generated by condensation of sulfuric acid contained in exhaust gas and ammonia gas is mixed due to a temperature drop in the wet desulfurization apparatus, and the residence time until this is introduced into the stagnant wet electrostatic precipitator This is based on the knowledge that, if a certain amount is ensured, a leakable ammonia gas can be reduced while producing harmless ammonium sulfate (acidic ammonium sulfate).

すなわち、上記目的を達成するために、本発明に係る排ガス処理方法は、排ガスを湿式脱硫して硫黄酸化物を除去した後、この脱硫排ガス中の硫酸ミスト量を求め、当該硫酸ミスト量と等量比１以下の濃度のアンモニアガスを混入して湿式電気集塵装置に通過させて硫酸ミストを除去することを特徴としている。   That is, in order to achieve the above-described object, the exhaust gas treatment method according to the present invention obtains the amount of sulfuric acid mist in the desulfurized exhaust gas after performing wet desulfurization of the exhaust gas to remove sulfur oxides, and the like. A feature is that ammonia gas having a concentration ratio of 1 or less is mixed and passed through a wet electrostatic precipitator to remove sulfuric acid mist.

また、本発明は、排ガスを湿式脱硫して硫黄酸化物を除去した後、この脱硫排ガスを湿式電気集塵装置に導入して硫酸ミストを除去する排ガス処理方法において、前記湿式電気集塵装置の前段で脱硫排ガス中にアンモニアガスを供給するとともに、前記湿式電気集塵装置の出口側でのアンモニアガス濃度を求め、前記電気集塵装置の前段で供給するアンモニアガス供給量を制御して前記濃度を設定範囲内に保持することを特徴としている。   The present invention also provides an exhaust gas treatment method in which exhaust gas is wet desulfurized to remove sulfur oxides, and then the desulfurized exhaust gas is introduced into a wet electrostatic precipitator to remove sulfuric acid mist. The ammonia gas is supplied into the desulfurization exhaust gas in the previous stage, the ammonia gas concentration on the outlet side of the wet electrostatic precipitator is obtained, and the ammonia gas supply amount supplied in the front stage of the electrostatic precipitator is controlled to adjust the concentration. Is maintained within the set range.

これらの場合において、湿式電気集塵装置に導入される前記脱硫排ガスとアンモニアガスの混合ガスの滞留時間を１秒以上に保持するようにすることが望ましい。   In these cases, it is desirable to maintain the residence time of the mixed gas of the desulfurization exhaust gas and ammonia gas introduced into the wet electrostatic precipitator for 1 second or more.

更に、本発明に係る排ガス処理設備は、排ガス中の硫黄酸化物を除去する湿式脱硫装置と、該湿式脱硫装置で脱硫した排ガスから硫酸ミストを除去する湿式電気集塵装置とを備えた排ガス処理設備において、前記湿式電気集塵装置に導入される排ガスにアンモニアガスを供給するアンモニアガス供給手段を設けたことを特徴とする。   Furthermore, an exhaust gas treatment facility according to the present invention includes an exhaust gas treatment device that includes a wet desulfurization device that removes sulfur oxides in the exhaust gas, and a wet electric dust collector that removes sulfuric acid mist from the exhaust gas desulfurized by the wet desulfurization device. The facility is characterized in that ammonia gas supply means for supplying ammonia gas to the exhaust gas introduced into the wet electrostatic precipitator is provided.

斯かる構成によれば、湿式電気集塵装置に導入される排ガスにアンモニアガスを供給したので、湿式電気集塵装置の内部において、排ガス中の硫酸ミストとアンモニアガスが反応して酸性硫安粒子となり、前記硫酸ミストより粒子径が大きくなる。これにより、湿式電気集塵装置において硫酸ミストの捕集効率を向上させることができる。   According to such a configuration, since ammonia gas is supplied to the exhaust gas introduced into the wet electrostatic precipitator, the sulfuric acid mist and ammonia gas in the exhaust gas react to form acidic ammonium sulfate particles inside the wet electrostatic precipitator. The particle size is larger than that of the sulfuric acid mist. Thereby, the collection efficiency of sulfuric acid mist can be improved in a wet type electrostatic precipitator.

また、本発明に係る排ガス処理設備を適用した場合、供給するアンモニアガスの濃度が高いほど、酸性硫安の生成効率は高くなるが、余剰のアンモニアガスは未反応のまま排ガス処理設備から放出されるため環境に悪影響を与える。よって、湿式電気集塵装置に流入する硫酸ミストの濃度（２０〜８０ｐｐｍ）と排ガス温度における反応効率から、アンモニアガス濃度は硫酸ミスト濃度に対して等量比１以下が好ましい。   Further, when the exhaust gas treatment facility according to the present invention is applied, the higher the concentration of ammonia gas to be supplied, the higher the production efficiency of acidic ammonium sulfate, but the excess ammonia gas is released from the exhaust gas treatment facility without being reacted. Therefore, it has an adverse effect on the environment. Therefore, from the concentration (20 to 80 ppm) of sulfuric acid mist flowing into the wet electrostatic precipitator and the reaction efficiency at the exhaust gas temperature, the ammonia gas concentration is preferably an equivalence ratio of 1 or less with respect to the sulfuric acid mist concentration.

更に、前記アンモニア供給ガス供給手段は、湿式電気集塵装置に導入されるアンモニアガスの上流側排ガス中での滞留時間が１秒以上とする位置に設定することにより、反応を確実にし、リークアンモニアガス濃度を低減することができる。   Furthermore, the ammonia supply gas supply means ensures the reaction by setting the residence time in the upstream exhaust gas of the ammonia gas introduced into the wet electrostatic precipitator to be 1 second or more, thereby leaking ammonia. The gas concentration can be reduced.

また、前記湿式電気集塵装置において、湿式電気集塵設備で回収される廃液に含まれる固形分と液体分を分離し、液体分からアンモニアガスを分離して入口ガスへ混合する配管設備を備えた構成としてもよい。この構成を採用することにより、アンモニアガスの再利用を図りつつ、もともとのアンモニアガス供給手段によるガス供給量を低減することができる。   The wet electrostatic precipitator further includes a piping facility that separates solids and liquids contained in the waste liquid collected by the wet electrostatic precipitator and separates ammonia gas from the liquid and mixes it with the inlet gas. It is good also as a structure. By adopting this configuration, it is possible to reduce the amount of gas supplied by the original ammonia gas supply means while reusing ammonia gas.

加えて、前記湿式電気集塵装置の後段にアンモニアガス濃度計を設置し、湿式電気集塵装置からの未反応アンモニアガスの濃度を測定し、前記湿式電気集塵装置の前段に供給するアンモニアガスの量を制限する調整手段を設けるようにしてもよい。   In addition, an ammonia gas concentration meter is installed downstream of the wet electrostatic precipitator, the concentration of unreacted ammonia gas from the wet electrostatic precipitator is measured, and the ammonia gas supplied to the front of the wet electrostatic precipitator Adjustment means for limiting the amount of the above may be provided.

本発明によれば、湿式電気集塵装置に供給される排ガス中にアンモニアガスを供給し、硫酸ミストを酸性硫安粒子にして粒径を大きくしたので、湿式脱硫装置にて発生した硫酸ミストを後段の湿式電気集塵装置にて効率よく捕集させることができる。   According to the present invention, ammonia gas is supplied into the exhaust gas supplied to the wet electrostatic precipitator, and the sulfuric acid mist is made acidic ammonium sulfate particles to increase the particle size. It can be efficiently collected with a wet electric dust collector.

以下添付図面に従って、本発明に係る排ガス処理方法及び設備の好ましい実施の形態について説明する。
図１は本実施形態に係る排ガス処理設備１０のフロー図である。
同図に示す実施形態に係る排ガス処理設備１０は、石油や重油等を燃料とするボイラ１２から排出される排ガスを無害化して処理するためのものである。 Preferred embodiments of an exhaust gas treatment method and equipment according to the present invention will be described below with reference to the accompanying drawings.
FIG. 1 is a flowchart of the exhaust gas treatment facility 10 according to the present embodiment.
The exhaust gas treatment facility 10 according to the embodiment shown in the figure is for detoxifying and treating exhaust gas discharged from a boiler 12 using petroleum, heavy oil or the like as fuel.

まず、排ガス処理設備１０の基本構成は次のようになっている。ボイラ１２の直後には脱硝装置１４が配置されており、ここで窒素酸化物が除去される。脱硝装置１４から排出されるガスの熱を利用してボイラ燃焼用空気を予熱するエアヒータ１６が設けられている。このエアヒータ１６にて燃焼用空気等の空気と熱交換により百数十度まで温度降下した排ガスは、乾式電気集塵装置１８に導入されるようになっており、ここで排ガス中に含まれる煤塵が捕集された後、湿式脱硫装置２０に導入される。湿式脱硫装置２０では、内部で消石灰や水酸化マグネシウム等のスラリーを噴霧することにより、主に排ガス中の二酸化硫黄などの硫黄酸化物を吸収除去する。次いで、湿式脱硫装置２０を経た排ガスは湿式電気集塵装置２２に導入され、ここで硫酸ミストとダストが除去された後、熱交換器２４を経て煙突２６から外部に排出されるものとなっている。これらの一連の処理装置間は排ガスダクト２８により接続され、排ガスを流通させるように構成されている。したがって、ボイラ１２から排出された排ガスは、乾式電気集塵装置１８で除塵され、湿式脱硫装置２０で脱硫され、湿式電気集塵装置２２で硫酸ミストとダストが除去されて大気に放出される。   First, the basic configuration of the exhaust gas treatment facility 10 is as follows. Immediately after the boiler 12, a denitration device 14 is disposed, where nitrogen oxides are removed. An air heater 16 for preheating boiler combustion air using the heat of the gas discharged from the denitration device 14 is provided. The exhaust gas whose temperature has dropped to a few hundred degrees by heat exchange with air such as combustion air in the air heater 16 is introduced into the dry electrostatic precipitator 18 where dust contained in the exhaust gas is introduced. Is collected and then introduced into the wet desulfurization apparatus 20. In the wet desulfurization apparatus 20, a slurry such as slaked lime or magnesium hydroxide is sprayed inside to absorb and remove mainly sulfur oxides such as sulfur dioxide in the exhaust gas. Next, the exhaust gas that has passed through the wet desulfurization apparatus 20 is introduced into a wet electrostatic precipitator 22 where the sulfuric acid mist and dust are removed and then discharged from the chimney 26 through the heat exchanger 24. Yes. A series of these processing apparatuses are connected by an exhaust gas duct 28, and the exhaust gas is circulated. Therefore, the exhaust gas discharged from the boiler 12 is dedusted by the dry electrostatic precipitator 18, desulfurized by the wet desulfurizer 20, and the sulfuric acid mist and dust are removed by the wet electrostatic precipitator 22, and released to the atmosphere.

また、湿式電気集塵装置２２には、アンモニアガスを供給することで生成される酸性硫安のダストと、洗浄水を分離する廃液処理装置２３が備えられており、ダスト分離後の廃液は循環して、洗浄水として再利用する構造となっている。分離後の酸性硫安ダストは、肥料として再利用される。   In addition, the wet electrostatic precipitator 22 is provided with a waste liquid treatment device 23 for separating acid ammonium sulfate dust generated by supplying ammonia gas and washing water, and the waste liquid after the dust separation is circulated. Thus, the structure is reused as cleaning water. The acidic ammonium sulfate dust after separation is reused as fertilizer.

このような基本構成において、特に本実施形態では、湿式脱硫装置２０と湿式電気集塵装置２２とを連通する排ガスダクト２８に対し、アンモニアガス供給装置３０のアンモニアガス供給ダクト３２が接続連通されている。   In such a basic configuration, particularly in this embodiment, the ammonia gas supply duct 32 of the ammonia gas supply device 30 is connected to the exhaust gas duct 28 that connects the wet desulfurization device 20 and the wet electrostatic precipitator 22. Yes.

上記湿式脱硫装置２０の内部では、消石灰や水酸化マグネシウム等のスラリーが排ガスに噴霧され、排ガス中の二酸化硫黄が吸収除去される。このとき、排ガスの温度は、飽和温度である数十度まで低下し、この温度低下の過程で、まず、排ガス中に含まれる硫酸が凝縮する。次いで、水分の飽和状態の近くまで排ガスの温度が低下した際に、前記ミストに水が凝縮し、硫酸濃度の低いミストが生成される。この硫酸ミストの粒子径は１ミクロン以下のサブミクロンオーダーで、湿式電気集塵装置２２にとって捕集しにくい大きさである。   Inside the wet desulfurization apparatus 20, a slurry such as slaked lime or magnesium hydroxide is sprayed on the exhaust gas, and sulfur dioxide in the exhaust gas is absorbed and removed. At this time, the temperature of the exhaust gas is reduced to a saturation temperature of several tens of degrees, and in the course of this temperature decrease, first, sulfuric acid contained in the exhaust gas is condensed. Next, when the temperature of the exhaust gas is lowered to near the saturated state of water, water is condensed in the mist, and a mist having a low sulfuric acid concentration is generated. The particle diameter of the sulfuric acid mist is in the submicron order of 1 micron or less, and is a size that is difficult for the wet electrostatic precipitator 22 to collect.

この硫酸ミストを含む排ガス中に、前記アンモニアガス供給装置３０によってアンモニアガスを供給すると酸性硫安が生成され、その粒子径は数ミクロンオーダー以上となり、湿式電気集塵装置２２にとって捕集容易となる。   When ammonia gas is supplied to the exhaust gas containing sulfuric acid mist by the ammonia gas supply device 30, acidic ammonium sulfate is generated, and the particle diameter thereof is on the order of several microns or more, which makes it easy for the wet electrostatic precipitator 22 to collect.

ところで、アンモニアガス供給装置３０から供給するアンモニアガス濃度は、硫酸ミストの濃度及び温度及び反応時間に依存し、湿式脱硫装置出口における排ガス温度約６０℃においては、反応時間を１秒以上とすることで、図２、および図３のように硫酸ミストの濃度に対して、ほぼ等量のアンモニアガス濃度で酸性硫安が生成されることを実験で見出した。   By the way, the concentration of ammonia gas supplied from the ammonia gas supply device 30 depends on the concentration and temperature of sulfuric acid mist and the reaction time. At an exhaust gas temperature of about 60 ° C. at the outlet of the wet desulfurization device, the reaction time should be 1 second or more. Thus, as shown in FIG. 2 and FIG. 3, it was found through experiments that acidic ammonium sulfate was produced at an ammonia gas concentration almost equal to the sulfuric acid mist concentration.

すなわち、硫酸ミストが２０ｐｐｍでは２０ｐｐｍが、８０ｐｐｍでは８０ｐｐｍが必要である。通常、湿式脱硫装置２０から出る排ガス中の硫酸ミストの濃度は、２０〜８０ｐｐｍの範囲で変動することから、アンモニアガス濃度は２０〜８０ｐｐｍが好ましい。   That is, 20 ppm is necessary for sulfuric acid mist of 20 ppm, and 80 ppm is necessary for 80 ppm. Usually, since the concentration of sulfuric acid mist in the exhaust gas discharged from the wet desulfurization apparatus 20 varies in the range of 20 to 80 ppm, the ammonia gas concentration is preferably 20 to 80 ppm.

また、アンモニアガスを供給する場合、硫酸ミストとアンモニアガスの反応に要する時間が必要で、排ガスの滞留時間に依存し、図３のような関係にあることを実験で見出した。入口硫酸ミスト濃度２０ｐｐｍに対して、アンモニアガス２０ｐｐｍを供給して滞留時間とリークアンモニアガス濃度の関係を調べた結果、滞留時間１．０秒以上で、リークアンモニアはほぼ横ばいで、反応が十分行われていることから、滞留時間は１．０秒以上が好ましい。   In addition, when ammonia gas is supplied, the time required for the reaction between sulfuric acid mist and ammonia gas is required, and it has been experimentally found that the relationship shown in FIG. 3 depends on the residence time of the exhaust gas. As a result of investigating the relationship between the residence time and leaked ammonia gas concentration by supplying 20 ppm of ammonia gas to the inlet sulfuric acid mist concentration of 20 ppm, the leaked ammonia was almost flat and the reaction was sufficiently performed when the residence time was 1.0 second or more. Therefore, the residence time is preferably 1.0 second or longer.

そこで、実施形態では、アンモニアガス供給装置３０は、供給したアンモニアガスが排ガス処理設備１０内に均一に分散するようノズル（図示せず）を配置し、そのときの排ガス中の硫酸ミスト濃度２０〜８０ｐｐｍに対して等量比１以下の濃度となるようにアンモニア供給量が制御管理される。この場合、硫酸ミストの量を直接測定することは実質的に困難であるので、湿式脱硫装置２０でのＳＯ2濃度を測定し、このＳＯ2から硫酸ミストに転換される率を実績値として求め、これから硫酸ミストの量を間接的に求めるようにすればよい。このため、ＳＯ2濃度測定器３４によって湿式脱硫装置２０内部のＳＯ2濃度を測定するようにしており、この測定値を制御手段３６に出力している。制御手段３６はアンモニアガス供給装置３０による供給量を制御するもので、測定結果によりミスト転換率実績値を格納した記録手段３８からデータを読み出し、硫酸ミスト濃度を換算し、これと等量のアンモニアガスを、アンモニアガス供給ダクト３２を通じて、排ガス中に導入するようにしている。 So, in embodiment, the ammonia gas supply apparatus 30 arrange | positions a nozzle (not shown) so that the supplied ammonia gas may disperse | distribute uniformly in the exhaust gas treatment equipment 10, and the sulfuric acid mist density | concentration in the exhaust gas at that time 20- The ammonia supply amount is controlled and managed so that the concentration ratio is 1 or less with respect to 80 ppm. In this case, since it is practically difficult to directly measure the amount of sulfuric acid mist, the SO 2 concentration in the wet desulfurization apparatus 20 is measured, and the conversion rate from this SO 2 to sulfuric acid mist is obtained as the actual value. From this, the amount of sulfuric acid mist may be obtained indirectly. Therefore, the SO 2 concentration measuring device 34 has to measure the SO 2 concentration in the wet desulfurization system 20, and outputs the measured value to the control means 36. The control means 36 controls the supply amount by the ammonia gas supply device 30. The control means 36 reads data from the recording means 38 storing the actual mist conversion rate value based on the measurement result, converts the sulfuric acid mist concentration, and the equivalent amount of ammonia. The gas is introduced into the exhaust gas through the ammonia gas supply duct 32.

また、湿式電気集塵装置２２の出口から排出される排ガス中のアンモニアガス濃度を検出する濃度計４０を設けることができる。そして、この濃度計４０により計測したアンモニアガス濃度が設定値内にあるか否かを判別し、これによって排ガス中の硫酸ミストに対しアンモニアガスが等量供給されているか否かを判定するようにすることができる。アンモニアガス濃度が規定濃度より多い場合には過剰供給であるとして制御手段３６によってアンモニアガス供給量を減量供給するようにすればよい。また、同時に、大気放出ガス中へのアンモニアガスによる放出微粒子濃度が規制値を超えないように、制御手段３６を通じてアンモニアガス供給量を調整することができる。これによって放出微粒子規制を設定範囲内に保持させることができる。   Further, a concentration meter 40 for detecting the ammonia gas concentration in the exhaust gas discharged from the outlet of the wet electrostatic precipitator 22 can be provided. Then, it is determined whether or not the ammonia gas concentration measured by the densitometer 40 is within a set value, thereby determining whether or not an equal amount of ammonia gas is supplied to the sulfuric acid mist in the exhaust gas. can do. When the ammonia gas concentration is higher than the specified concentration, it is determined that the supply is excessive and the ammonia gas supply amount may be reduced by the control means 36. At the same time, the supply amount of ammonia gas can be adjusted through the control means 36 so that the concentration of emitted fine particles by the ammonia gas into the atmospheric emission gas does not exceed the regulation value. As a result, the emission fine particle restriction can be kept within the set range.

更に、上述したように、前記アンモニアガス供給装置３０によってアンモニアガスを排ガス中に混合させた後、湿式電気集塵装置２２に導入されるまでの管路滞留時間は１秒以上が望ましい。このため、アンモニアガス供給ダクト３２の接続点は、混合ガスが湿式電気集塵装置２２の入口に至るまでの通流時間が１秒以上となる位置となるように設定する。これは接続点から湿式電気集塵装置２２までの管路長を内部流速によって調整できるような構成としてもよい。   Further, as described above, it is desirable that the pipe residence time from mixing ammonia gas into the exhaust gas by the ammonia gas supply device 30 and introducing the ammonia gas into the wet electrostatic precipitator 22 is 1 second or more. For this reason, the connection point of the ammonia gas supply duct 32 is set so that the flow time until the mixed gas reaches the inlet of the wet electrostatic precipitator 22 is 1 second or longer. This may be configured such that the pipe length from the connection point to the wet electrostatic precipitator 22 can be adjusted by the internal flow rate.

これにより、湿式電気集塵装置２２には、アンモニアガスと硫酸ミストの混合された排ガスが適正濃度であって適正滞留時間を確保して供給するようにしている。   Thus, the wet electric dust collector 22 is supplied with the exhaust gas mixed with ammonia gas and sulfuric acid mist having an appropriate concentration and ensuring an appropriate residence time.

また、この実施形態では、上述したように、湿式電気集塵装置２２には、アンモニアガスを供給することで生成される酸性硫安のダストと、洗浄水を分離する廃液処理装置２３が備えられている。この廃液処理装置２３は、例えば、図４に示すようなアンモニアストリッピング法を用いた構成とすればよい。すなわち、固液分離された廃液４２を中和槽４４へ供給し、これに苛性ソーダ溶液４６を添加し、発生するアンモニアガスを空気４８でパージして、第１放散塔５０の塔頂部へ供給し、液は第２放散塔５２の塔頂部へ供給するようにしている。第２放散塔５２の塔底部へ放散用空気５４と、スチーム５６を供給する。これにより、第１放散塔５０の塔頂からはアンモニア、スチーム、酸素、窒素の放散ガス５８が発生し、塔底からはアンモニア性窒素が除去された再生液６０が抽出される。再生液６０はスプレー水として再利用することができ、湿式電気集塵装置２２のスプレイ手段（図示せず）に戻し配管６２を介して循環させている。一方、この実施形態では、分離されたアンモニアガスを含む放散ガス５８の一部を補充配管６４により前記アンモニアガス供給装置３０に導入するようにして、硫酸ミストを酸性硫安の生成に再利用するようにしている。残余の放散ガスはアンモニア酸化塔６６に供給して窒素に変換処理する。このアンモニア酸化塔６６は、ガス分散器６８、アンモニア酸化触媒層７０、および、脱硝触媒層７２の順に配列されたもので、この例では、前記アンモニア酸化触媒層６６と脱硝触媒層７２との間にスロート部を有するアンモニアガス混合器７４を設け、前記アンモニア酸化塔６６に導入するアンモニア含有ガスを２分割し、一方をアンモニア酸化触媒層７０に導入し、他方を前記ガス導入管からアンモニアガス混合器７４に導入するよう構成している。   In this embodiment, as described above, the wet electrostatic precipitator 22 is provided with the waste liquid treatment device 23 for separating the acid ammonium sulfate dust generated by supplying ammonia gas and the washing water. Yes. The waste liquid treatment apparatus 23 may be configured to use, for example, an ammonia stripping method as shown in FIG. That is, the solid-liquid separated waste liquid 42 is supplied to the neutralization tank 44, the caustic soda solution 46 is added thereto, the generated ammonia gas is purged with air 48, and supplied to the top of the first stripping tower 50. The liquid is supplied to the top of the second stripping tower 52. Dissipation air 54 and steam 56 are supplied to the bottom of the second diffusion tower 52. As a result, ammonia, steam, oxygen and nitrogen emission gas 58 is generated from the top of the first diffusion tower 50, and the regenerated liquid 60 from which ammonia nitrogen has been removed is extracted from the tower bottom. The regenerated liquid 60 can be reused as spray water, and is circulated through the return pipe 62 to the spray means (not shown) of the wet electrostatic precipitator 22. On the other hand, in this embodiment, a part of the diffused gas 58 containing the separated ammonia gas is introduced into the ammonia gas supply device 30 through the supplementary pipe 64 so that the sulfuric acid mist is reused for the production of acidic ammonium sulfate. I have to. The remaining emitted gas is supplied to the ammonia oxidation tower 66 and converted to nitrogen. The ammonia oxidation tower 66 is arranged in the order of a gas distributor 68, an ammonia oxidation catalyst layer 70, and a denitration catalyst layer 72. In this example, the ammonia oxidation tower 66 is disposed between the ammonia oxidation catalyst layer 66 and the denitration catalyst layer 72. Is provided with an ammonia gas mixer 74 having a throat portion, the ammonia-containing gas introduced into the ammonia oxidation tower 66 is divided into two, one is introduced into the ammonia oxidation catalyst layer 70, and the other is mixed with ammonia gas from the gas introduction pipe. It is configured to be introduced into the container 74.

また、上記アンモニアトリッピング法に限らず、生物処理法により、湿式電気集塵装置２２から排出される廃液を再生してスプレー水として再利用させることもできる。この場合は、図５に示すように、アンモニアを含有する廃水をダスト分離処理を行う膜分離装置７６に通し、次いで硝化菌固定化担体を有するアンモニア硝化槽７８に供給する。その後、脱窒槽８０に供給することでアンモニアが分離された再生液が生成される。   Moreover, the waste liquid discharged from the wet electrostatic precipitator 22 can be regenerated and reused as spray water by a biological treatment method as well as the above ammonia tripping method. In this case, as shown in FIG. 5, waste water containing ammonia is passed through a membrane separation device 76 that performs dust separation treatment, and then supplied to an ammonia nitrification tank 78 having a nitrifying bacteria immobilization carrier. Thereafter, a regenerated liquid from which ammonia is separated is generated by supplying the denitrification tank 80.

次に上記の如く構成された排ガス処理設備１０の作用について説明する。
ボイラ１２から排出された排ガスは、脱硝装置１４を通過後、エアヒータ１６によって百数十度まで冷却された後、乾式電気集塵装置１８に導入され、静電気によって排ガス中のダストが除去される。 Next, the operation of the exhaust gas treatment facility 10 configured as described above will be described.
The exhaust gas discharged from the boiler 12 passes through the denitration device 14, is cooled to hundreds of degrees by the air heater 16, is then introduced into the dry electrostatic precipitator 18, and dust in the exhaust gas is removed by static electricity.

次いで、ダストが除去された排ガスは、湿式脱硫装置２０に導入される。湿式脱硫装置２０の内部では、消石灰や水酸化マグネシウム等のスラリーが排ガスに噴霧され、排ガス中の二酸化硫黄が吸収除去される。このとき、排ガスの温度は、飽和温度である数十度まで低下し、この温度低下の過程で、まず、排ガス中に含まれる硫酸が凝縮する。次いで、水分の飽和状態の近くまで排ガスの温度が低下した際に、前記ミストに水が凝縮し、硫酸濃度の低いミストが生成される。この硫酸ミストの粒子径は１ミクロン以下のサブミクロンオーダーで、湿式電気集塵装置２２にとって捕集しにくい大きさである。   Next, the exhaust gas from which the dust has been removed is introduced into the wet desulfurization apparatus 20. Inside the wet desulfurization apparatus 20, slurry such as slaked lime or magnesium hydroxide is sprayed on the exhaust gas, and sulfur dioxide in the exhaust gas is absorbed and removed. At this time, the temperature of the exhaust gas is reduced to a saturation temperature of several tens of degrees, and in the course of this temperature decrease, first, sulfuric acid contained in the exhaust gas is condensed. Next, when the temperature of the exhaust gas is lowered to near the saturated state of water, water is condensed in the mist, and a mist having a low sulfuric acid concentration is generated. The particle diameter of the sulfuric acid mist is in the submicron order of 1 micron or less, and is a size that is difficult for the wet electrostatic precipitator 22 to collect.

この硫酸ミストを含む排ガス中に、アンモニアガス供給装置３０からアンモニアガスが供給されることにより酸性硫安が生成され、その粒子径は数ミクロンオーダー以上となり、湿式電気集塵装置２２にとって捕集容易となるので高い捕集効率で除去される。また、アンモニアガスが供給される位置は、湿式電気集塵装置２２に導入されるまでの滞留時間が１．０秒以上となるように設定されているので、図３に示すように、硫酸ミストとアンモニアガスを十分に反応させることができ、これによりリークアンモニアガスの発生量を大幅に低減することができる。   By supplying ammonia gas from the ammonia gas supply device 30 to the exhaust gas containing the sulfuric acid mist, acidic ammonium sulfate is generated, the particle diameter becomes more than several microns, and it is easy for the wet electrostatic precipitator 22 to collect. Therefore, it is removed with high collection efficiency. Further, the position where the ammonia gas is supplied is set so that the residence time until it is introduced into the wet electrostatic precipitator 22 is 1.0 second or longer. And ammonia gas can sufficiently react with each other, whereby the generation amount of leaked ammonia gas can be greatly reduced.

本発明の実施形態に係る排ガス処理設備の全体構成図である。1 is an overall configuration diagram of an exhaust gas treatment facility according to an embodiment of the present invention. 硫酸ミスト濃度とアンモニアガス濃度の関係を示すグラフ図である。It is a graph which shows the relationship between sulfuric acid mist density | concentration and ammonia gas density | concentration. アンモニアガスと硫酸ミストの滞留時間とリークアンモニアガス濃度の関係を示すグラフ図である。It is a graph which shows the relationship between the residence time of ammonia gas and sulfuric acid mist, and leak ammonia gas concentration. 湿式電気集塵装置のアンモニアトリッピング法を用いた廃液処理装置の構成図である。It is a block diagram of the waste liquid processing apparatus using the ammonia tripping method of a wet electric dust collector. 湿式電気集塵装置の生物処理法を用いた廃液処理装置の構成図である。It is a block diagram of the waste liquid processing apparatus using the biological treatment method of a wet electric dust collector.

符号の説明Explanation of symbols

１０………排ガス処理設備、１２………ボイラ、１４………脱硝装置、１６………エアヒータ、１８………乾式電気集塵装置、２０………湿式脱硫装置、２２………湿式電気集塵装置、２３………廃液処理装置、２４………熱交換器、２６………煙突、２８………排ガスダクト、３０………アンモニアガス供給装置、３２………アンモニアガス供給ダクト、３４………ＳＯ2濃度測定器、３６………制御手段、３８………記録手段、４０………アンモニアガス濃度計、４２………廃液、４４………中和槽、４６………苛性ソーダ溶液、４８………空気、５０………第１放散塔、５２………第２放散塔、５４………放散用空気、５６………スチーム、５８………放散ガス、６０………再生液、６２………戻し配管、６４………補充配管、６６………アンモニア酸化塔、６８………ガス分散器、７０………アンモニア酸化触媒層、７２………脱硝触媒層、７４………アンモニアガス混合器。 10 ......... Exhaust gas treatment equipment, 12 ......... Boiler, 14 ......... Denitration device, 16 ...... Air heater, 18 ......... Dry electrostatic precipitator, 20 ...... Wet desulfurization device, 22 ......... Wet Electric dust collector, 23 ......... Waste liquid treatment device, 24 ......... Heat exchanger, 26 ......... Chimney, 28 ...... Exhaust gas duct, 30 ...... Ammonia gas supply device, 32 ......... Ammonia gas supply duct, 34 ......... SO 2 concentration meter, 36 ......... control means 38 ......... recording means 40 ......... ammonia gas concentration meter, 42 ......... waste, 44 ......... neutralization tank, 46 ……… Caustic soda solution, 48 ……… Air, 50 ……… First diffusion tower, 52 ……… Second diffusion tower, 54 ……… Dissipation air, 56 ……… Steam, 58 ……… Emission gas 60 ......... regenerated liquid, 62 ......... return piping, 64 ......... replenishment piping, 66 ... ... ammonia oxidation tower, 68 ......... gas distributor, 70 ......... ammonia oxidation catalyst layer, 72 ......... denitration catalyst layer, 74 ......... ammonia gas mixer.

Claims (8)

排ガスを湿式脱硫して硫黄酸化物を除去した後、この脱硫排ガス中の硫酸ミスト量を求め、当該硫酸ミスト量と等量比１以下の濃度のアンモニアガスを混入して湿式電気集塵装置に通過させて硫酸ミストを除去することを特徴とする排ガス処理方法。   After the exhaust gas is wet desulfurized to remove sulfur oxides, the amount of sulfuric acid mist in the desulfurized exhaust gas is obtained, and ammonia gas having a concentration equal to or less than 1 with the sulfuric acid mist amount is mixed into the wet electric dust collector. An exhaust gas treatment method characterized by removing sulfuric acid mist by passing it through. 排ガスを湿式脱硫して硫黄酸化物を除去した後、この脱硫排ガスを湿式電気集塵装置に導入して硫酸ミストを除去する排ガス処理方法において、前記湿式電気集塵装置の前段で脱硫排ガス中にアンモニアガスを供給するとともに、前記湿式電気集塵装置の出口側でのアンモニアガス濃度を求め、前記電気集塵装置の前段で供給するアンモニアガス供給量を制御して前記濃度を設定範囲内に保持することを特徴とする排ガス処理方法。   In an exhaust gas treatment method in which exhaust gas is wet desulfurized to remove sulfur oxides, and then this desulfurized exhaust gas is introduced into a wet electrostatic precipitator to remove sulfuric acid mist, in the desulfurized exhaust gas before the wet electrostatic precipitator, While supplying ammonia gas, obtain the ammonia gas concentration at the outlet side of the wet electrostatic precipitator, and control the amount of ammonia gas supplied at the front stage of the electrostatic precipitator to keep the concentration within the set range An exhaust gas treatment method comprising: 湿式電気集塵装置に導入される前記脱硫排ガスとアンモニアガスの混合ガスの滞留時間を１秒以上に保持することを特徴とする請求項１または２記載の排ガス処理方法。   The exhaust gas treatment method according to claim 1 or 2, wherein a residence time of the mixed gas of the desulfurized exhaust gas and ammonia gas introduced into the wet electrostatic precipitator is maintained at 1 second or longer. 排ガス中の硫黄酸化物を除去する湿式脱硫装置と、該湿式脱硫装置で脱硫した排ガスから硫酸ミストを除去する湿式電気集塵装置とを備えた排ガス処理設備において、前記湿式電気集塵装置に導入される排ガスにアンモニアガスを供給するアンモニアガス供給手段を設けたことを特徴とする排ガス処理設備。   An exhaust gas treatment facility comprising a wet desulfurization device that removes sulfur oxides in exhaust gas and a wet electric dust collector that removes sulfuric acid mist from the exhaust gas desulfurized by the wet desulfurization device. An exhaust gas treatment facility comprising ammonia gas supply means for supplying ammonia gas to exhaust gas to be discharged. 前記アンモニアガス供給手段はアンモニアガス濃度が硫酸ミスト濃度に対して等量比を１以下とする制御手段を設けてあることを特徴とする請求項４記載の排ガス処理設備。   5. The exhaust gas treatment facility according to claim 4, wherein the ammonia gas supply means is provided with a control means for setting the equivalence ratio of the ammonia gas concentration to the sulfuric acid mist concentration to 1 or less. 前記アンモニア供給ガス供給手段は、湿式電気集塵装置に導入されるアンモニアガスの上流側排ガス中での滞留時間が１秒以上とする位置に設定していることを特徴とする請求項４記載の排ガス処理設備。   The said ammonia supply gas supply means is set to the position which makes residence time in the upstream exhaust gas of the ammonia gas introduce | transduced into a wet-type electrostatic precipitator into 1 second or more. Exhaust gas treatment equipment. 前記湿式電気集塵装置において、湿式電気集塵設備で回収される廃液に含まれる固形分と液体分を分離し、液体分からアンモニアガスを分離して入口ガスへ混合する配管設備を備えたことを特徴とする請求項４記載の排ガス処理設備。   The wet electrostatic precipitator includes a piping facility that separates solids and liquids contained in the waste liquid collected by the wet electrostatic precipitator, separates ammonia gas from the liquid, and mixes it with the inlet gas. The exhaust gas treatment facility according to claim 4, wherein 前記湿式電気集塵装置の後段にアンモニアガス濃度計を設置し、湿式電気集塵装置からの未反応アンモニアガスの濃度を測定し、前記湿式電気集塵装置の前段に供給するアンモニアガスの量を制限する調整手段を設けたことを特徴とする請求項１記載の排ガス処理設備。   An ammonia gas concentration meter is installed downstream of the wet electrostatic precipitator, the concentration of unreacted ammonia gas from the wet electrostatic precipitator is measured, and the amount of ammonia gas supplied to the upstream of the wet electrostatic precipitator is determined. 2. The exhaust gas treatment facility according to claim 1, further comprising adjusting means for limiting.
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