JP3640674B2 - Method for separating gaseous pollutants from heat treatment gas - Google Patents

Method for separating gaseous pollutants from heat treatment gas Download PDF

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JP3640674B2
JP3640674B2 JP51717096A JP51717096A JP3640674B2 JP 3640674 B2 JP3640674 B2 JP 3640674B2 JP 51717096 A JP51717096 A JP 51717096A JP 51717096 A JP51717096 A JP 51717096A JP 3640674 B2 JP3640674 B2 JP 3640674B2
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mixer
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JPH10509914A (en
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オーマン，ステファン
ブリングフォルス，ニルス
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アルストム、パワー、ホールディング、アクチエボラーグ
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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
    • B01D53/508—Sulfur oxides by treating the gases with solids
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/81—Solid phase processes

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Description

本発明は、煙道ガスのような熱処理ガスから二酸化硫黄のようなガス状の汚染物質を分離する方法であって、熱処理ガスは、ガス状の汚染物質を分離可能な塵に変えるため、ガス状の汚染物質との間で反応性を有する粒状の吸収材が湿った状態で熱処理ガスに導入される接触反応器に通され、さらに熱処理ガスは、その内部で熱処理ガスから塵が分離されるとともに浄化処理済みガスが排出される塵分離器に通され、この塵分離器内にて分離された塵の一部は、その内部で混合がなされるとともに湿潤化のために水が供給されるミキサーに通され、さらにこの塵の一部は、新たな吸収材の追加分とともに熱処理ガスに導入されることにより吸収材として再循環する方法に関する。
熱処理ガスからガス状の汚染物質を分離する上述した方法は例えば、SE−8504675−３およびSE−8904106−５において知られている。これら２つの文献によえば、新たな吸収材としては好ましくは粒状の消石灰（水酸化カルシウム）が用いられる。この吸収材は塵分離器内にて熱処理ガスから分離された塵と混合され、さらにこの混合物には接触反応器内の煙道ガスに湿った状態で導入されるよう水が供給される。消石灰は比較的高価であり、このような消石灰の代わりに比較的安価な生石灰（酸化カルシウム）を用いるための各種の試みがなされている。これらの試みにおいては、生石灰が浄化工程に導入される前に、生石灰を消化するプラント、すなわち酸化カルシウムと水とを反応させて水酸化カルシウムを形成させるプラントを用いなければならない。このような石灰消化プラントは高価であり、このことの消石灰から生石灰に代替した際に予想される利益が出ないということを意味している。
本発明の目的は、生石灰を消化するための高価でかつ別個のプラントを必要とすることなく消石灰を生石灰に代替することができる、熱処理ガスからガス状の汚染物質を分離する方法を提供することを目的とする。
本発明によれば、このような目的は導入部に述べた種類の方法であって、生石灰が新たな吸収材として追加され、かつ塵分離器内にて分離された塵の大半はミキサーに対して略連続的な流れとして供給および排出され、この塵は、ミキサー内における湿った状態での生石灰の総滞留時間が、生石灰とミキサーに供給される水とが略完全に反応し、かつ生石灰から消石灰が形成されるのに十分な時間となるよう、ミキサー内で長時間にわたって留まり、かつ多数回にわたって再循環することを特徴とする方法により達成される。
生石灰の形態をなす新たな吸収材は、好ましくはミキサーに供給されるが、塵分離器内にて分離されミキサーに供給される塵の一部に追加されるようにしてもよい。また生石灰は、接触反応器内の煙道ガス内に直接導入されるようにしてもよい。
混合された塵を流体化させ、これにより混合を促進させるために、好ましくはミキサーに空気流が供給される。
以下、本発明について添付図面を参照してより詳細に説明する。ここで図面は、石炭燃焼主要加熱プラントからの煙道ガスを浄化するためのプラントであって、本発明による方法を実施るすための設備が設けられた浄化プラントを模式的に示したものである。
図面は、石炭燃焼主要加熱プラント１からの煙道ガスを浄化するためのプラントを示し、前記煙道ガスはフライアッシュのような塵と、二酸化硫黄のようなガス状の汚染物質とを含んでいる。予熱装置２は、熱い煙道ガスから、ダクト2aを介してファン３により主要加熱プラント１に供給される燃焼空気へ熱を移動させるために配置されている。
熱い煙道ガスはダクト４を通って塵分離器５に搬送される。図示された実施例において塵分離器５は、煙道ガスを通すことにより浄化を行う３つの連続した集塵器ユニットを有する静電集塵器である。このようにして浄化された煙道ガスはダクト６を介して煙道ガスファン７に通され、この煙道ガスファン７はダクト８を介して煙道ガスが大気に放出されるよう煙突９に煙道ガスを供給する。塵分離器はまた、バッグフィルタであってもよい。
ダクト４は接触反応器10を形成する垂直部分を備えている。ミキサー11は接触反応器10の下方部分と連通している。ミキサー11は煙道ガス内のガス状の汚染物質との間で反応性を有する粒状の吸収材を湿った状態で接触反応器10の下方部分に導入する。この吸収材はガス状の汚染物質を集塵器５内にて分離される塵に変える。集塵器５内にて分離された塵粒子は集塵器ユニットのホッパ12内で集められる。集められた塵粒子の大半は、以下に詳細に説明する方法によりシステム内で再循環する。集められた塵粒子の残りは、詳細には説明しないが、例えばウォームコンベヤにより外部に搬送される。
ミキサー11はSE−9404104−３に記載された種類のものである。従って、ミキサー11は本質的に二重底の箱形状を有している。これら２つの底のうち上部のものは張力がかけられたポリエステルの流体化布（fluidising cloth）からなる２つの底の間には、空気供給管15を通ってミキサー11内の粒状の吸収材を流体化させるための空気が導かれるチャンバ14が設けられている。ミキサー11には、ミキサーの上方部分に配置された水供給管16およびノズル17を通って水が供給される。混合される粒状の材料はミキサーの入口側端部にある２つの材料インレット18および19を通ってミキサー11に供給される。ミキサー11はさらに、協働して用いられる２つの平行なアジテータ（このうち１つのみが図面に示されている）であって各々が水平シャフトとこれに取り付けられた複数の傾いた楕円板とを有するアジテータからなる機械的な混合機構20を備えている。ミキサー11の出口側端部は、よく混合されかつ湿った吸収材を流し口21から接触反応器10に連続的に供給するため、接触反応器10まで延びている。
システム内で再循環する、集塵器ユニットのホッパ12内で集められた塵粒子の一部分は、インレット19を通ってミキサー11に供給される。粒状の生石灰（酸化カルシウム）は、インレット19を通って供給される塵粒子に混合させるため、インレット18を通ってミキサー11に供給される。混合物はノズル17から供給される水により湿潤化される。ノズル17から供給される水はまた、ミキサー11に供給される生石灰を消化するためのものでもある。機械的な混合機構20の構造、およびミキサー11に供給される材料粒子の流体化により、ミキサー11は、ミキサー11の流し口21を通って吸収材として連続的に接触反応器10に供給される、均一に湿らされた均一な混合物を生成する。ミキサー11内での材料粒子の滞留時間は約５乃至60秒、とりわけ10乃至20秒である。
ミキサー11内での材料粒子の上述したような滞留時間（10乃至20秒）、すなわち石灰粒子が湿った状態にある時間は、生石灰と消化のために追加される水とが完全に反応し、かつ生石灰から消石灰が形成されるのに十分な時間とはなっていない。このような反応は比較的遅く、数分を要する。
ここで、以下に示す理論上の実例により、本発明についてより詳細に説明する。この実例では、図面の点Ａ、ＢおよびＣ、すなわちそれぞれがミキサー11の前方にあるダクト４内、ミキサー11の後方にある反応器10のうち集塵器５の入口側、および集塵器５の出口側に該当する位置を支配する条件が示されている。

Figure 0003640674
点Ａでの塵はほとんどフライアッシュであり、これに対し点Ｂでの塵はフライアッシュおよび吸収材である。
点Ｄでは、単位時間あたり2930kgの塵が排出され、このうち2,000kgはフライアッシュである。
この実例では従って、消化される生石灰を含む粒状の吸収材は、点Ｄで排出される前にシステム内で平均して約35
Figure 0003640674
回にわたって循環している。従って、生石灰を消化するのに十分な、ミキサー11内での吸収材の総滞留時間は350乃至700秒、すなわち約６乃至12分である。
上述した実例における水の総消費量は3,366（l/h）であり、このうち152（l/h）が石灰の消化に必要とされる。このような量の水が消費されたときには、ミキサー11から排出される吸収材の水分含有量は約６％である。しかしながら水分含有量は、混合物の組成に応じて好ましくは２乃至15％の範囲で変化する。
上述した実例において、点Ａでの煙道ガスのフライアッシュ含有量が０、すなわち点Ｄでの排出量が930（kg/h）である場合には、上述した場合からの類推により、その循環数は、約110
Figure 0003640674
であり、このことから滞留時間は1,100乃至2,200秒、すなわち約18乃至37分となる。The present invention is a method for separating gaseous pollutants such as sulfur dioxide from a heat treatment gas such as flue gas, wherein the heat treatment gas converts the gaseous pollutants into separable dust, The particulate absorbent having reactivity with the pollutant in the form of moisture is passed through a contact reactor introduced into the heat treatment gas in a wet state, and the heat treatment gas further separates dust from the heat treatment gas therein. A part of the dust separated in the dust separator is mixed and supplied with water for wetting. Further, the present invention relates to a method in which a part of the dust is passed through a mixer and further recycled as an absorbent material by being introduced into the heat treatment gas together with the addition of new absorbent material.
The above-described method for separating gaseous contaminants from the heat treatment gas is known, for example, in SE-8504675-3 and SE-8904106-5. According to these two documents, granular slaked lime (calcium hydroxide) is preferably used as the new absorbent material. This absorbent material is mixed with dust separated from the heat treatment gas in the dust separator, and this mixture is further supplied with water so as to be introduced wet into the flue gas in the catalytic reactor. Slaked lime is relatively expensive, and various attempts have been made to use relatively inexpensive quick lime (calcium oxide) instead of such slaked lime. In these attempts, a plant that digests quicklime, that is, a plant that reacts calcium oxide with water to form calcium hydroxide, must be used before the quicklime is introduced into the purification process. Such lime digestion plants are expensive, meaning that the expected benefits of replacing slaked lime with quick lime are not achieved.
The object of the present invention is to provide a method for separating gaseous pollutants from heat treated gas, which can replace slaked lime with quick lime without the need for an expensive and separate plant for digesting quick lime. With the goal.
According to the invention, such an object is a method of the kind mentioned in the introduction, in which quicklime is added as a new absorbent and most of the dust separated in the dust separator is directed to the mixer. The dust is supplied and discharged as a substantially continuous stream, and the total amount of wet lime residence time in the mixer is almost completely reacted by the quick lime and the water supplied to the mixer. This is achieved by a process characterized by staying in the mixer for a long time and recirculating a number of times so that there is sufficient time for slaked lime to form.
The new absorbent material in the form of quicklime is preferably supplied to the mixer, but may be added to a portion of the dust separated in the dust separator and supplied to the mixer. Quicklime may also be introduced directly into the flue gas in the contact reactor.
An air stream is preferably supplied to the mixer to fluidize the mixed dust and thereby facilitate mixing.
Hereinafter, the present invention will be described in more detail with reference to the accompanying drawings. Here, the drawing schematically shows a purification plant for purifying flue gas from a coal-fired main heating plant and provided with equipment for carrying out the method according to the invention. is there.
The drawing shows a plant for purifying flue gas from a coal-fired main heating plant 1, said flue gas comprising dust such as fly ash and gaseous pollutants such as sulfur dioxide. Yes. The preheating device 2 is arranged to transfer heat from the hot flue gas to the combustion air supplied to the main heating plant 1 by the fan 3 via the duct 2a.
Hot flue gas is conveyed through the duct 4 to the dust separator 5. In the illustrated embodiment, the dust separator 5 is an electrostatic precipitator having three consecutive precipitator units that purify by passing flue gas. The flue gas purified in this way is passed through a duct 6 to a flue gas fan 7, which passes through a duct 8 into the chimney 9 so that the flue gas is released to the atmosphere. Supply flue gas. The dust separator may also be a bag filter.
The duct 4 is provided with a vertical part forming a catalytic reactor 10. The mixer 11 is in communication with the lower part of the catalytic reactor 10. The mixer 11 introduces into the lower part of the catalytic reactor 10 in a wet state a granular absorbent material that is reactive with gaseous pollutants in the flue gas. This absorber converts gaseous pollutants into dust that is separated in the dust collector 5. The dust particles separated in the dust collector 5 are collected in the hopper 12 of the dust collector unit. Most of the collected dust particles are recirculated in the system in the manner described in detail below. Although the collected dust particles are not described in detail, they are conveyed to the outside by, for example, a worm conveyor.
The mixer 11 is of the type described in SE-9404104-3. Therefore, the mixer 11 essentially has a double bottom box shape. Of these two bottoms, the upper one is between the two bottoms made of tensioned polyester fluidizing cloth, passing the air supply pipe 15 between the particulate absorbent in the mixer 11. A chamber 14 into which air for fluidization is guided is provided. The mixer 11 is supplied with water through a water supply pipe 16 and a nozzle 17 arranged in the upper part of the mixer. The granular material to be mixed is fed to the mixer 11 through two material inlets 18 and 19 at the inlet end of the mixer. The mixer 11 further includes two parallel agitators (only one of which is shown in the drawing) used in cooperation, each having a horizontal shaft and a plurality of inclined elliptical plates attached thereto. The mechanical mixing mechanism 20 which consists of an agitator which has is provided. The outlet end of the mixer 11 extends to the contact reactor 10 in order to continuously supply a well-mixed and moist absorbent to the contact reactor 10 from the outlet 21.
A portion of the dust particles collected in the hopper 12 of the dust collector unit that recirculates in the system is fed to the mixer 11 through the inlet 19. The granular quicklime (calcium oxide) is supplied to the mixer 11 through the inlet 18 for mixing with dust particles supplied through the inlet 19. The mixture is wetted by water supplied from the nozzle 17. The water supplied from the nozzle 17 is also for digesting quicklime supplied to the mixer 11. Due to the structure of the mechanical mixing mechanism 20 and the fluidization of the material particles supplied to the mixer 11, the mixer 11 is continuously supplied to the catalytic reactor 10 as an absorbent through the outlet 21 of the mixer 11. To produce a homogeneous mixture, evenly moistened. The residence time of the material particles in the mixer 11 is about 5 to 60 seconds, in particular 10 to 20 seconds.
The residence time of the material particles in the mixer 11 as described above (10 to 20 seconds), i.e., the time during which the lime particles are in a wet state, allows the quick lime and water added for digestion to react completely, And it is not enough time for slaked lime to be formed from quicklime. Such a reaction is relatively slow and takes several minutes.
The present invention will now be described in more detail with the following theoretical examples. In this example, the points A, B and C in the drawing, ie in the duct 4 respectively in front of the mixer 11, the inlet side of the dust collector 5 of the reactor 10 behind the mixer 11, and the dust collector 5. The conditions governing the position corresponding to the exit side of are shown.
Figure 0003640674
The dust at point A is mostly fly ash, whereas the dust at point B is fly ash and absorber.
At point D, 2930 kg of dust is discharged per unit time, of which 2,000 kg is fly ash.
In this example, therefore, the granular absorbent containing quicklime to be digested averages about 35 in the system before being discharged at point D.
Figure 0003640674
It is circulating over time. Thus, the total residence time of the absorbent in the mixer 11 sufficient to digest quicklime is 350 to 700 seconds, or about 6 to 12 minutes.
The total water consumption in the above example is 3,366 (l / h), of which 152 (l / h) is required for lime digestion. When such an amount of water is consumed, the moisture content of the absorbent discharged from the mixer 11 is about 6%. However, the moisture content preferably varies between 2 and 15% depending on the composition of the mixture.
In the above example, when the fly ash content of the flue gas at point A is 0, that is, the discharge amount at point D is 930 (kg / h), the circulation is made by analogy from the above case. Number is about 110
Figure 0003640674
Therefore, the residence time is 1,100 to 2,200 seconds, that is, about 18 to 37 minutes.

Claims (7)

煙道ガスのような熱処理ガスから二酸化硫黄のようなガス状の汚染物質を分離する方法であって、熱処理ガスは、ガス状の汚染物質を分離可能な塵に変えるため、ガス状の汚染物質との間で反応性を有する粒状の吸収材が湿った状態で熱処理ガスに導入される接触反応器（10）に通され、さらに熱処理ガスは、その内部で熱処理ガスから塵が分離されるとともに浄化処理済みガスが排出される塵分離器（５）に通され、この塵分離器（５）内にて分離された塵の一部は、その内部で混合がなされるとともに湿潤化のために水が供給されるミキサー（11）に通され、さらにこの塵の一部は、新たな吸収材の追加分とともに熱処理ガスに導入されることにより吸収材として再循環する方法において、生石灰が新たな吸収材として追加され、かつ塵分離器（５）内にて分離された塵の大半はミキサー（11）に対して略連続的な流れとして供給および排出され、かつ、塵分離器（５）内にて分離された塵の大半と新たな吸収剤として追加された生石灰とにより形成される材料粒子の流れは、ミキサー（11）内での材料粒子の１回の通過あたりの滞留時間が、生石灰とミキサー（１）に供給された水とが完全に反応するのには十分な時間でないような態様で、ミキサー（11）を通って移動し、かつ、この材料粒子の流れは、ミキサー（11）内における湿った状態での生石灰の総滞留時間が、生石灰とミキサーに供給される水とが略完全に反応し、かつ生石灰から消石灰が形成されるのに十分な時間となるよう、ミキサーを通って多数回にわたって再循環し、ミキサー内で長時間にわたって留まることを特徴とする方法。A method for separating gaseous pollutants such as sulfur dioxide from a heat treatment gas such as flue gas, wherein the heat treatment gas converts the gaseous pollutants into separable dust and thus gaseous pollutants. Is passed through a contact reactor (10) that is introduced into the heat treatment gas in a wet state, and further the heat treatment gas has dust separated from the heat treatment gas therein. A part of the dust separated in the dust separator (5) is passed through the dust separator (5) from which the purified gas is discharged, and is mixed in the dust separator for wetting. In a method in which water is passed through a mixer (11) and a part of this dust is recirculated as an absorbent by being introduced into the heat treatment gas together with the addition of new absorbent, Added as an absorbent and dust Most of the dust separated in the separator (5) is supplied and discharged as a substantially continuous flow to the mixer (11), and most of the dust separated in the dust separator (5). And the flow of material particles formed by fresh lime added as a new absorbent, the residence time per pass of the material particles in the mixer (11) is supplied to the quick lime and the mixer (1). In such a manner that it does not have sufficient time to react completely with water, and the material particle stream is in a wet state in the mixer (11). The total quick lime residence time is recirculated through the mixer a number of times so that the quick lime and the water supplied to the mixer are almost completely reacted and slaked lime is formed from the quick lime. Stay in the mixer for a long time Wherein the. 生石灰の形態をなす新たな吸収材は、ミキサー（11）に供給されることを特徴とする請求項１記載の方法。2. The process as claimed in claim 1, wherein fresh absorbent material in the form of quicklime is fed to the mixer (11). 生石灰の形態をなす新たな吸収材は、塵分離器（５）内にて分離されミキサー（11）に供給される塵の一部に追加されることを特徴とする請求項１記載の方法。2. The process as claimed in claim 1, wherein the new absorbent in the form of quicklime is added to a part of the dust that is separated in the dust separator (5) and fed to the mixer (11). 生石灰の形態をなす新たな吸収材は、接触反応器（10）内の煙道ガス内に直接導入されることを特徴とする請求項１記載の方法。2. The process as claimed in claim 1, wherein the new absorbent material in the form of quicklime is introduced directly into the flue gas in the contact reactor (10). 混合された塵を流体化させるために、ミキサー（11）に空気流が供給されることを特徴とする請求項１乃至４のいずれか記載の方法。5. A method according to claim 1, wherein an air stream is supplied to the mixer (11) to fluidize the mixed dust. ミキサー（11）内での材料粒子の１回の通過あたりの滞留時間は５乃至60秒であることを特徴とする、請求項１記載の方法。2. A method according to claim 1, characterized in that the residence time per pass of the material particles in the mixer (11) is 5 to 60 seconds. ミキサー（11）内での材料粒子の１回の通過あたりの滞留時間は10乃至20秒であることを特徴とする、請求項６記載の方法。7. A process according to claim 6, characterized in that the residence time per pass of the material particles in the mixer (11) is 10 to 20 seconds.
JP51717096A 1994-11-28 1995-11-24 Method for separating gaseous pollutants from heat treatment gas Expired - Lifetime JP3640674B2 (en)

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