JP2002355531A - Method of treating exhaust gas in cement production - Google Patents
Method of treating exhaust gas in cement productionInfo
- Publication number
- JP2002355531A JP2002355531A JP2001392854A JP2001392854A JP2002355531A JP 2002355531 A JP2002355531 A JP 2002355531A JP 2001392854 A JP2001392854 A JP 2001392854A JP 2001392854 A JP2001392854 A JP 2001392854A JP 2002355531 A JP2002355531 A JP 2002355531A
- Authority
- JP
- Japan
- Prior art keywords
- exhaust gas
- mercury
- dust
- temperature
- volatile metal
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B7/00—Hydraulic cements
- C04B7/36—Manufacture of hydraulic cements in general
- C04B7/364—Avoiding environmental pollution during cement-manufacturing
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Biodiversity & Conservation Biology (AREA)
- Ecology (AREA)
- Environmental & Geological Engineering (AREA)
- Environmental Sciences (AREA)
- Public Health (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Treating Waste Gases (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、セメントの製造工
程から排出される排ガス中に含まれる水銀等を効率よく
除去し、水銀等を除去した集塵ダストをセメント原料に
再利用する排ガスの処理方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for treating exhaust gas, which efficiently removes mercury and the like contained in exhaust gas discharged from a cement manufacturing process, and reuses dust-collected dust from which mercury and the like have been removed as a raw material for cement. About the method.
【０００２】[0002]
【従来の技術】近年、廃棄物の最終処分場の残存容量が
逼迫しており、しかも新たな最終処分場の建設も進ま
ず、廃棄物の埋立処理には限界がある。従って、廃棄物
を資源として再生することは社会的に重要な課題であ
り、セメント産業においても廃棄物の再利用が求められ
ている。このような現状下で、各種の汚泥、焼却灰など
の廃棄物をセメント原料や燃料として使用する機会が増
えている。しかし、これらの廃棄物には重金属類が多少
なりとも含有されており、このためセメント製造工程に
持ち込まれる重金属類の量が増大することが懸念され
る。これらの廃棄物に含まれる重金属類のうち、水銀、
亜鉛、セレン等、およびこれらの塩化物等は、セメント
製造工程の高温部において揮発し、ガス中に含有され
る。その後、ガスの温度が低下するのに伴いガス中に含
有されるダストの表面にこれらの重金属が析出し、ある
いは重金属やその化合物自身の微粒子となる。これらの
ダストや微粒子は煙道の電気集塵器(ＥＰ)で捕集され、
排ガス中から除去される。2. Description of the Related Art In recent years, the remaining capacity of a final disposal site for waste has become tight, and construction of a new final disposal site has not progressed. Therefore, recycling waste as a resource is an important social issue, and the cement industry is also demanding the reuse of waste. Under such circumstances, opportunities to use various kinds of waste such as sludge and incinerated ash as cement raw materials and fuels are increasing. However, these wastes contain heavy metals at all, and there is a concern that the amount of heavy metals brought into the cement manufacturing process will increase. Among the heavy metals contained in these wastes, mercury,
Zinc, selenium, etc., and their chlorides, etc. are volatilized in the high temperature part of the cement production process and are contained in the gas. Then, as the temperature of the gas decreases, these heavy metals precipitate on the surface of dust contained in the gas, or become fine particles of the heavy metal or its compound itself. These dusts and particulates are collected by an electric dust collector (EP) in the flue,
It is removed from the exhaust gas.
【０００３】[0003]
【発明が解決しようとする課題】捕集されたダスト(集
塵ダスト)をセメント製造原料の一部として際利用する
場合、集塵ダストに含まれる揮発性の重金属の大部分は
クリンカー焼成炉の高温部で再び揮発し、ガス中に含有
されて再び排ガス系に導かれる。このうち水銀は揮発性
が高く、高温でガス化し易いためにクリンカには殆ど含
有されず、排ガス中に含まれ、一部は排ガスと共に系外
に排出されるが、大部分は排ガス系を循環することにな
る。このため、排ガス中の水銀を処理する手段を設けな
いと、原料から持ち込まれる水銀量が増大するのに伴っ
て排ガス中の水銀濃度が次第に高くなり、排ガス温度の
低下に伴って水銀がダクトに析出したり、系外への水銀
排出量が増える等の問題を生じる。When the collected dust (dust dust) is used as a part of a raw material for cement production, most of the volatile heavy metals contained in the dust dust are collected by the clinker firing furnace. It volatilizes again in the high-temperature portion, is contained in the gas, and is led again to the exhaust gas system. Of these, mercury has high volatility and is easily gasified at high temperatures, so it is hardly contained in clinker, it is contained in exhaust gas, and part is discharged out of the system together with exhaust gas, but most of it circulates in the exhaust gas system Will do. For this reason, if there is no means for treating mercury in the exhaust gas, the mercury concentration in the exhaust gas will gradually increase as the amount of mercury brought in from the raw materials increases, and the mercury will be introduced into the duct as the exhaust gas temperature decreases. Problems such as precipitation and an increase in the amount of mercury discharged out of the system occur.
【０００４】本発明は、このようなセメント製造工程か
ら排出される排ガス中に含まれる水銀等の揮発性金属を
効率よく除去し、水銀の排出量を抑制すると共に集塵ダ
ストをセメント原料の一部に再利用するうえで好都合な
処理方法を提供する。The present invention efficiently removes volatile metals such as mercury contained in exhaust gas discharged from such a cement production process, suppresses the amount of mercury discharged, and reduces dust collection dust as one of cement raw materials. It provides a convenient processing method for reuse in the department.
【０００５】すなわち、本発明は以下の構成からなるセ
メント製造排ガスの処理方法に関する。 （１）セメント製造工程の排ガスから捕集した集塵ダス
トを加熱炉に導き、集塵ダストに含まれる揮発性金属成
分の揮発温度以上に加熱して上記揮発性金属成分をガス
化して除去し、揮発性金属成分を除去した集塵ダストを
セメント原料の一部に用いることを特徴とするセメント
製造排ガスの処理方法。 （２）揮発性金属成分が水銀であり、水銀蒸気を含む排
ガスを水銀除去装置に導いて排ガスから水銀を除去する
上記(1)に記載する排ガスの処理方法。 （３）排ガスから水銀を除去する方法が、酸性溶液ない
し酸化性溶液に水銀を吸収させる方法である上記(2)に
記載する排ガスの処理方法。 （４）排ガスから水銀を除去する方法が、硫黄または金
属硫化物による吸着除去である上記(2)に記載する排ガ
スの処理方法 （５）排ガスから水銀を除去する方法が、活性炭または
活性炭を担持した吸着媒体による吸着除去である上記
(2)に記載する排ガスの処理方法。 （６）排ガスから水銀を除去する方法が、水銀と反応す
る金属または水銀と反応する金属を担持した吸着媒体に
よる吸着除去である上記(2)に記載する排ガスの処理方
法。 （７）ガス化した金属成分を含む高温ガスを冷却部に導
いて揮発性金属成分の析出温度以下に冷却し、これを液
化ないし固化してガス中から分離することによって排ガ
ス中の揮発性金属成分の濃度を低減する上記(1)に記載
する排ガスの処理方法。 （８）セメント製造工程において排出された熱排ガスに
よって加熱炉を加熱する上記(1)〜(7)の何れかに記載す
る排ガスの処理方法。That is, the present invention relates to a method for treating exhaust gas from cement production having the following constitution. (1) The collected dust collected from the exhaust gas of the cement manufacturing process is guided to a heating furnace, and heated to a temperature equal to or higher than the volatile temperature of the volatile metal component contained in the collected dust to gasify and remove the volatile metal component. A method for treating exhaust gas from cement production, comprising using dust collected from a volatile metal component as a part of a cement raw material. (2) The method for treating exhaust gas as described in (1) above, wherein the volatile metal component is mercury, and the exhaust gas containing mercury vapor is guided to a mercury removing device to remove mercury from the exhaust gas. (3) The method for treating exhaust gas according to the above (2), wherein the method for removing mercury from the exhaust gas is a method for absorbing mercury into an acidic solution or an oxidizing solution. (4) The method for treating exhaust gas as described in (2) above, wherein the method for removing mercury from exhaust gas is adsorption removal using sulfur or metal sulfide. (5) The method for removing mercury from exhaust gas uses activated carbon or activated carbon. Absorption removal by the absorbed adsorption medium
The method for treating exhaust gas described in (2). (6) The method for treating exhaust gas according to the above (2), wherein the method for removing mercury from the exhaust gas is adsorption removal using an adsorption medium carrying a metal that reacts with mercury or a metal that reacts with mercury. (7) The high-temperature gas containing the gasified metal component is guided to the cooling section, cooled to a temperature lower than the deposition temperature of the volatile metal component, and liquefied or solidified and separated from the gas to thereby remove the volatile metal in the exhaust gas. The method for treating exhaust gas according to the above (1), wherein the concentration of the component is reduced. (8) The method for treating exhaust gas according to any one of the above (1) to (7), wherein the heating furnace is heated by the hot exhaust gas discharged in the cement production process.
【０００６】[0006]
【発明の実施の形態】以下、本発明を実施形態に基づい
て具体的に説明する。本発明の処理方法は、セメント製
造工程の排ガスから捕集した集塵ダストを加熱炉に導
き、集塵ダストに含まれる揮発性金属成分の揮発温度以
上に加熱して上記揮発性金属成分をガス化して除去し、
揮発性金属成分を除去した集塵ダストをセメント原料の
一部に用いることを特徴とするセメント製造排ガスの処
理方法である。特に揮発性金属成分である水銀につい
て、集塵ダストを加熱して水銀をガス化し、集塵ダスト
から分離する一方、水銀蒸気を含む排ガスを水銀除去装
置に導いて排ガスから水銀を除去する排ガスの処理方法
である。DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, the present invention will be specifically described based on embodiments. In the treatment method of the present invention, the dust collected from the exhaust gas of the cement manufacturing process is guided to a heating furnace, and heated to a temperature equal to or higher than the volatilization temperature of the volatile metal component contained in the dust, and the volatile metal component is gasified. And remove
This is a method for treating exhaust gas from cement production, comprising using dust collected from which volatile metal components have been removed as part of a cement raw material. In particular, for mercury, a volatile metal component, the dust collected is heated to gasify the mercury and separated from the dust, while the exhaust gas containing mercury vapor is led to a mercury removal device to remove mercury from the exhaust gas. Processing method.
【０００７】本発明に係る処理方法の一例を図１に示
す。図示するように、本発明の処理系統には、セメント
製造工程の排ガス路１０に設置した電気集塵機２１、電
気集塵機２１によって捕集した集塵ダストを受け入れる
加熱炉３０、加熱炉３０から排出された高温排ガスから
水銀等を除去する装置３１、水銀除去装置３１から排出
された処理ガスを系外あるいは排ガス路等に送り出す吸
引ファン３２が設けられている。排ガス路１０の末端に
は煙突２２が設置されている。FIG. 1 shows an example of a processing method according to the present invention. As shown in the drawing, in the treatment system of the present invention, an electric precipitator 21 installed in an exhaust gas path 10 in a cement manufacturing process, a heating furnace 30 for receiving dust collected by the electric precipitator 21, and an exhaust gas discharged from the heating furnace 30. A device 31 for removing mercury and the like from the high-temperature exhaust gas, and a suction fan 32 for sending the processing gas discharged from the mercury removing device 31 out of the system or to an exhaust gas path or the like are provided. A chimney 22 is provided at the end of the exhaust gas passage 10.
【０００８】セメント焼成キルンなどの製造工程から排
出された排ガスは、排ガス路１０を通じて電気集塵機２
１に導入され、ここで排ガス中に含まれるダストが捕集
される。本発明の処理対象となる排ガスはセメント製造
工程から排出されるものであれば何れでも良い。集塵機
２１の種類は限定されないが、大量の排ガスを処理でき
るという点からは電気集塵機が好ましい。集塵機２１に
導入される排ガスの温度は概ね１００〜１５０℃である
ので、排ガスに含まれる水銀、セレン、カドミウム、亜
鉛などの揮発性金属またはその塩化物などの揮発性金属
化合物、（これらを揮発性金属成分と云う）の大部分は
ダストの表面に析出し、あるいは微粒子となって排ガス
中に含まれる。これを集塵機２１によって捕集する。Exhaust gas discharged from a manufacturing process such as a cement firing kiln passes through an exhaust gas passage 10 to the electric precipitator 2.
1, where dust contained in the exhaust gas is collected. Exhaust gas to be treated according to the present invention may be any as long as it is discharged from the cement production process. Although the type of the dust collector 21 is not limited, an electric dust collector is preferable because a large amount of exhaust gas can be treated. Since the temperature of the exhaust gas introduced into the dust collector 21 is generally 100 to 150 ° C., a volatile metal compound such as mercury, selenium, cadmium, zinc, or a volatile metal compound such as a chloride thereof contained in the exhaust gas, Most of the metal component is precipitated on the surface of dust or becomes fine particles and is contained in exhaust gas. This is collected by the dust collector 21.
【０００９】捕集したダストおよび揮発性金属成分の析
出物（これらを集塵ダストと云う）を加熱炉３０に導入
する。加熱炉３０は内容物を加熱できるものであれば形
式を問わないが、例えばロータリーキルンの形式や、内
部に粉砕・混合用の媒体を有するミルの形式などを用い
ることができる。なお、内部にスクリューフィーダ３０
ａを備えたものが集塵ダストの加熱の均一性や搬送性の
点で優れているのでより好ましい。The collected dust and deposits of volatile metal components (these are referred to as dust dust) are introduced into a heating furnace 30. The heating furnace 30 may be of any type as long as it can heat the contents. For example, a rotary kiln type or a mill type having a pulverizing / mixing medium therein may be used. The screw feeder 30 is provided inside.
Those provided with a are more preferable because they are excellent in the uniformity of heating and the transportability of the dust collection dust.
【００１０】加熱炉の３０の一端から装入された集塵ダ
スト２５は炉内を搬送される間に水銀などの揮発性金属
成分の揮発温度以上に加熱され、揮発性金属成分がガス
化する。具体的には、概ね３００〜５００℃に加熱する
のが好ましい。因みに１mmHgの蒸気圧を生じる温度は、
水銀が約１２６℃、セレン、砒素およびカドミウムがそ
れぞれ約３５６℃〜約３９４℃、亜鉛が４８７℃であ
り、また塩化アンチモン(SbCl3)が約４９℃、塩化水銀
(HgCl2)が約１３６℃、塩化錫(SnCl2)が約３１６℃、塩
化亜鉛(ZnCl2)が約４２８℃である。従って、３００〜
５００℃の加熱下において概ねこれらが揮発する。な
お、加熱温度が３００℃より低いと水銀等の除去が困難
であり、５００℃以上では水銀等を除去するには特に問
題はないが、加熱エネルギーの割に効果は変わらず、不
経済である。３５０℃〜５００℃であればさらに効率よ
く集塵ダストから水銀等を除去することができる。The dust collected from one end of the heating furnace 30 is heated to a temperature higher than the volatilization temperature of volatile metal components such as mercury while being transported in the furnace, and the volatile metal components are gasified. . Specifically, it is preferable to heat to about 300 to 500 ° C. By the way, the temperature at which the vapor pressure of 1 mmHg occurs is
About 126 ° C for mercury, about 356 ° C to about 394 ° C for selenium, arsenic and cadmium, 487 ° C for zinc, about 49 ° C for antimony chloride (SbCl 3 ), and about 49 ° C for mercury chloride.
(HgCl 2 ) is about 136 ° C., tin chloride (SnCl 2 ) is about 316 ° C., and zinc chloride (ZnCl 2 ) is about 428 ° C. Therefore, 300-
Under heating at 500 ° C., these generally evaporate. When the heating temperature is lower than 300 ° C., it is difficult to remove mercury and the like. When the heating temperature is 500 ° C. and higher, there is no particular problem in removing mercury and the like, but the effect is not changed for the heating energy and is uneconomical. . If the temperature is 350 ° C. to 500 ° C., mercury and the like can be more efficiently removed from the dust collection dust.
【００１１】加熱炉３０の熱源は炉内に水銀等を持ち込
むようなものでなければ何れの熱源でもよい。例えば、
ニクロム線、カンタル線、SiC発熱体、白金線、石油バ
ーナー、ガスバーナー、セメント焼成キルンから排出さ
れた熱排ガスによる廃熱(以下、キルン廃熱)などが挙げ
られる。具体的には、各種発熱体は加熱炉外周にまきつ
けて使用し、またキルン廃熱は加熱炉外周にキルン排ガ
スを導入するようにすればよい。石油バーナーやガスバ
ーナーは加熱炉の内部または炉外周にバーナーを設置し
てもよい。加熱炉３０によって水銀等を除去した集塵ダ
スト２５は加熱炉３０の排出口から取り出され、セメン
ト原料の粉砕機２０、または粉砕後の原料粉末に戻して
再利用することができる。The heat source of the heating furnace 30 may be any heat source as long as mercury or the like is not brought into the furnace. For example,
Nichrome wire, Kanthal wire, SiC heating element, platinum wire, oil burner, gas burner, waste heat from hot exhaust gas discharged from a cement kiln (hereinafter, kiln waste heat) and the like. Specifically, various heating elements may be used around the heating furnace, and kiln waste heat may be introduced into the kiln exhaust gas around the heating furnace. The oil burner or the gas burner may be provided with a burner inside or outside the heating furnace. The dust dust 25 from which mercury or the like has been removed by the heating furnace 30 is taken out from the outlet of the heating furnace 30 and can be returned to the pulverizer 20 of the cement raw material or the raw material powder after the pulverization for reuse.
【００１２】加熱炉３０から排出された高温の排ガスは
水銀除去部３１に導かれる。水銀除去部３１には、吸収
液を用いたガス吸収装置、または吸着剤を用いたガス吸
着装置を用いることができる。吸収液を用いたガス吸収
装置としては、例えば、充填塔、流動層スクラバー、ス
プレー塔、サイクロンスクラバー、気泡塔、漏れ棚塔な
どが挙げられる。吸収液としては酸性溶液および／また
は酸化性溶液が用いられる。集塵ダストを加熱した高温
の排ガスに含まれる水銀は主として元素状であるので水
銀を吸収する液は酸性かまたは酸化性のものを用いる。
酸性溶液としては硝酸またはその水溶液、硫酸またはそ
の水溶液、またはこれらの混合液が適当であえる。酸化
性溶液は、酸化性を有する水溶液であればよいが、例え
ば、硝酸またはその水溶液、王水、過マンガン酸カリウ
ム水溶液、過マンガン酸ナトリウム水溶液、重クロム酸
カリウム水溶液、重クロム酸ナトリウム水溶液、過酸化
水素水、またはこれらの混合液などが適当である。酸性
溶液と酸化性溶液を任意の割合で混合した溶液でも良
い。The high-temperature exhaust gas discharged from the heating furnace 30 is led to a mercury removing unit 31. For the mercury removing unit 31, a gas absorbing device using an absorbing liquid or a gas absorbing device using an adsorbent can be used. Examples of the gas absorbing device using the absorbing liquid include a packed tower, a fluidized bed scrubber, a spray tower, a cyclone scrubber, a bubble tower, a leak tray tower, and the like. An acidic solution and / or an oxidizing solution is used as the absorbing solution. Since the mercury contained in the high-temperature exhaust gas obtained by heating the dust collection dust is mainly elemental, an acidic or oxidizing liquid is used as the liquid for absorbing mercury.
As the acidic solution, nitric acid or an aqueous solution thereof, sulfuric acid or an aqueous solution thereof, or a mixture thereof may be suitable. The oxidizing solution may be any aqueous solution having an oxidizing property, for example, nitric acid or an aqueous solution thereof, aqua regia, an aqueous solution of potassium permanganate, an aqueous solution of sodium permanganate, an aqueous solution of potassium dichromate, an aqueous solution of sodium dichromate, Hydrogen peroxide or a mixture thereof is suitable. A solution in which an acidic solution and an oxidizing solution are mixed at an arbitrary ratio may be used.
【００１３】吸着剤を用いたガス吸着装置としては、例
えば、カートリッジ式固定相吸着装置、連続クロスフロ
ー式移動層吸着装置などを用いることができる。吸着剤
としては、硫黄または金属硫化物、活性炭または活性炭
を担持した吸着媒体、水銀と反応する金属または水銀と
反応する金属を担持した吸着媒体などが用いられる。硫
黄または金属硫化物は水銀と反応して硫化水銀を生成
し、加熱炉から排出された高温ガスから効率よく水銀を
除去することができる。金属硫化物は水銀よりイオン化
傾向の大きい金属の硫化物であれば特に限定されず、例
えば、硫化ナトリウム、硫化カリウム、硫化鉄、硫化亜
鉛などを用いることができる。硫黄または金属硫化物の
形状は、特に限定されず、粉末状、粒状、ハニカム状な
どいずれの形状でも使用できるが、ハニカム状であれば
通気ガスの圧力損失が低減でき、より好ましい。As a gas adsorption device using an adsorbent, for example, a cartridge type stationary phase adsorption device, a continuous cross flow type moving bed adsorption device and the like can be used. Examples of the adsorbent include sulfur or metal sulfide, activated carbon or an adsorption medium supporting activated carbon, an adsorption medium supporting a metal that reacts with mercury or a metal that reacts with mercury, and the like. Sulfur or metal sulfide reacts with mercury to produce mercury sulfide, and mercury can be efficiently removed from high-temperature gas discharged from a heating furnace. The metal sulfide is not particularly limited as long as it is a metal sulfide having a higher ionization tendency than mercury. For example, sodium sulfide, potassium sulfide, iron sulfide, zinc sulfide and the like can be used. The shape of sulfur or metal sulfide is not particularly limited, and any shape such as powder, granule, and honeycomb can be used. A honeycomb shape is more preferable because the pressure loss of the ventilation gas can be reduced.
【００１４】活性炭は比表面積が概ね５００〜１０００
ｍ2/gと極めて大きく、その表面に多量の水銀を吸着す
ることができるため、活性炭を用いて加熱炉から排出さ
れた高温ガスから効率よく水銀を除去することができ
る。活性炭は粉末状であると嵩比重が小さく取扱い難い
ので、活性炭を適当な担体に担持させて使用しても差し
支えない。なお、活性炭を使用する場合、活性炭による
吸着部を適当な温度、例えば５０℃以下に冷却して水銀
の吸着効果を高めるのが好ましい。Activated carbon has a specific surface area of about 500 to 1000.
Since it is as large as m 2 / g and a large amount of mercury can be adsorbed on the surface, mercury can be efficiently removed from the high-temperature gas discharged from the heating furnace using activated carbon. Activated carbon in powder form has a low bulk specific gravity and is difficult to handle, so that activated carbon may be supported on a suitable carrier for use. When using activated carbon, it is preferable to increase the mercury adsorption effect by cooling the activated carbon adsorption section to an appropriate temperature, for example, 50 ° C. or lower.
【００１５】水銀は白金、鉄、マンガン、コバルト、ニ
ッケルを除く多くの金属と反応してアマルガムを作るた
め、水銀と反応する金属を用いて加熱炉から排出された
高温ガスから効率よく水銀を除去することができる。水
銀と反応する金属としては、金、銀、銅、亜鉛、アルミ
ニウムなどが挙げられる。水銀と反応する金属の形状
は、特に限定されないが、例えば、粒状、コイル状、繊
維状、ベルサドル状、ラシヒリング状、ハニカム状など
が挙げられ、ハニカム状であれば通気ガスの圧力損失が
低減でき、好ましい。また、水銀と反応する金属を適当
な担体に担持させて使用しても良い。Since mercury reacts with many metals other than platinum, iron, manganese, cobalt and nickel to form amalgam, the metal that reacts with mercury is used to efficiently remove mercury from the high-temperature gas discharged from the heating furnace. can do. Examples of the metal that reacts with mercury include gold, silver, copper, zinc, and aluminum. The shape of the metal that reacts with mercury is not particularly limited, and includes, for example, granules, coils, fibers, bell saddles, Raschig rings, honeycombs, and the like. ,preferable. Further, a metal that reacts with mercury may be used by being supported on a suitable carrier.
【００１６】これら吸着剤の使用量は吸着すべき水銀の
モル数の１０倍以上が好ましく、１００倍以上であれば
水銀の除去効率を格段に高めることができる。水銀除去
部３１から排出されたガスは吸引ファン３２を通じて系
外に導かれる。この水銀が除去されたガスは、水銀濃度
が日本産業衛生学会勧告値（0.05mg/m3以下）などの規
制値より低いものは大気に排出することができる。ある
いはセメント製造工程または加熱炉３０の導入空気とし
て系内に戻し、循環させても良い。The amount of the adsorbent used is preferably at least 10 times the number of moles of mercury to be adsorbed, and if it is at least 100 times, the efficiency of removing mercury can be remarkably increased. The gas discharged from the mercury removing unit 31 is led out of the system through the suction fan 32. The gas from which mercury has been removed can be discharged to the atmosphere if the concentration of mercury is lower than a regulated value such as the value recommended by the Japan Society for Occupational Health (0.05 mg / m 3 or less). Alternatively, the air may be returned to the system as air introduced into the cement manufacturing process or the heating furnace 30 and circulated.
【００１７】以上の水銀除去装置３１の他に、ガス化し
た揮発性金属成分を冷却して除去する手段を設けても良
い。冷却部は、例えば、外周に冷却ジャケットを有し、
下部に傾斜板を設けた構造のものなどが用いることがで
きる。冷却部に導かれた揮発性金属成分のガスはその析
出温度以下に冷却される。具体的には例えば５０℃以下
に冷却され、例えば、水銀は液化して傾斜板表面に析出
し、またセレン、カドミウムなどは固化し、微粒子とな
って冷却部の底部に堆積する。冷却部の温度は５０℃よ
り高くてもガス中から水銀を除去することはできるが、
温度が高いとガス中に残存する水銀量が多くなり、効率
均に水銀をガス中から除去できないので、冷却温度は５
０℃以下が適当であり、低ければ低い方がよい。なお、
ダスト中の揮発性金属の含有量によってガス流量を調整
するのが好ましい。In addition to the mercury removing device 31 described above, means for cooling and removing gasified volatile metal components may be provided. The cooling unit has, for example, a cooling jacket on the outer periphery,
For example, one having a structure in which an inclined plate is provided at a lower portion can be used. The volatile metal component gas led to the cooling unit is cooled to a temperature lower than its deposition temperature. Specifically, it is cooled to, for example, 50 ° C. or less, for example, mercury liquefies and precipitates on the surface of the inclined plate, and selenium, cadmium and the like solidify and become fine particles and deposit on the bottom of the cooling unit. Even if the temperature of the cooling unit is higher than 50 ° C, mercury can be removed from the gas,
If the temperature is high, the amount of mercury remaining in the gas increases, and the mercury cannot be removed from the gas uniformly.
A temperature of 0 ° C. or lower is appropriate, and a lower temperature is better. In addition,
It is preferable to adjust the gas flow rate according to the volatile metal content in the dust.
【００１８】冷却部の底に溜まった水銀等は定期的に取
り出す。一方、冷却部から排出されたガスは吸引ファン
を通じて系外に導く。この冷却手段によって排ガス中の
揮発性金属成分の濃度を、例えば、水銀３０mg/m3Ｎ以
下、亜鉛０.０５０mg/m3Ｎ以下、カドミウム０.００１m
g/m3Ｎ以下に低減することができる。この冷却ガスは集
塵機２１の前に戻し、集塵機２１を再び経由して排出さ
せるのが好ましい。このような循環系によって、排ガス
中に含まれる水銀などの揮発性金属成分濃度を大幅に低
減することができる。The mercury and the like accumulated at the bottom of the cooling unit are periodically removed. On the other hand, the gas discharged from the cooling unit is led out of the system through the suction fan. By this cooling means, the concentration of the volatile metal component in the exhaust gas is reduced to, for example, 30 mg / m 3 N or less of mercury, 0.050 mg / m 3 N or less of zinc, and 0.001 m 2 of cadmium.
g / m 3 N or less. This cooling gas is preferably returned to the front of the dust collector 21 and discharged via the dust collector 21 again. With such a circulation system, the concentration of volatile metal components such as mercury contained in exhaust gas can be significantly reduced.
【００１９】[0019]
【実施例】以下、本発明を実施例によって具体的に示
す。 〔実施例１〜８〕セメント製造工場の捕集した集塵ダス
ト1kgを両端が開口した試験管（80mmφ×1000mm）の中
央部に充填し、管状炉を用い、表１に示す温度で30分間
加熱した。このとき試験管の片側開口部から流量0.5L/m
inの空気を導入し、他端から排出したガスを表１に示す
５種の水銀除去装置に導いて水銀を除去した。吸収液を
用いた水銀除去装置は容量250mlのインピンジャーに吸
収液50mlを入れたものを二本連結した構造とし、吸着剤
を用いた水銀除去装置ははホウ珪酸ガラス製の管に吸着
剤を１０ｇ詰めて吸着剤の両端を石英ウールで固定した
構造とした。吸収剤の硝酸、吸着剤の硫黄(粉末状)、硫
化鉄(粉末状)、活性炭(粉末状)、銅(粒状)は何れも関東
化学製品を用いた。水銀除去装置を通過したガス中の水
銀濃度は日本インスツルメンツ社製品の水銀分析装置(A
M-2D)を用いて測定した。また、加熱処理前後の集塵ダ
ストに含まれる水銀は日本インスツルメンツ社製品の水
銀分析装置(SP-3D)を用いて測定した。なお、加熱ガス
の平均水銀量は供給空気量、未処理集塵ダスト中の水銀
量および加熱処理後の集塵ダストに含まれる水銀残量に
基づいて算出した。集塵ダストに含まれる水銀含有量と
処理効果を表１に示す。何れの実施例でも集塵ダストの
水銀をほとんど除去することができ、かつ加熱ガス中の
水銀も極めて高効率に除去することができた。EXAMPLES The present invention will be specifically described below with reference to examples. [Examples 1 to 8] 1 kg of collected dust collected at a cement manufacturing plant was filled in the center of a test tube (80 mmφ × 1000 mm) having both ends opened, and the tube furnace was used for 30 minutes at a temperature shown in Table 1. Heated. At this time, the flow rate from one side of the test tube is 0.5 L / m
In air was introduced, and the gas discharged from the other end was led to five types of mercury removal devices shown in Table 1 to remove mercury. The mercury removal device using the absorbing solution has a structure in which two 250 ml impingers containing 50 ml of the absorbing solution are connected to each other, and the mercury removing device using the adsorbent uses an adsorbent in a tube made of borosilicate glass. 10 g was packed, and both ends of the adsorbent were fixed with quartz wool. Kanto Chemical Products were used for nitric acid as the absorbent, sulfur (powder), iron sulfide (powder), activated carbon (powder), and copper (granular) for the adsorbent. The mercury concentration in the gas that passed through the mercury removal device was measured by a mercury analyzer (A
M-2D). The mercury contained in the dust collected before and after the heat treatment was measured using a mercury analyzer (SP-3D) manufactured by Nippon Instruments. The average amount of mercury in the heated gas was calculated based on the amount of supplied air, the amount of mercury in the untreated collected dust, and the remaining amount of mercury in the collected dust after the heat treatment. Table 1 shows the mercury content of the dust collected and the treatment effect. In each of the examples, mercury in dust collected was almost completely removed, and mercury in the heated gas was also removed very efficiently.
【００２０】[0020]
【表１】 [Table 1]
【００２１】〔実施例９〕セメント製造テストプラント
で捕集した集塵ダストを図１に示すシステムに導いて水
銀を加熱除去し、水銀を除去した集塵ダストを再びセメ
ントプラントに戻し、その他は通常どおりの条件でセメ
ントを生産した。なおセメント原料中の水銀の量、およ
び廃棄物の添加量を調整して、表２に示す値となるよう
にした。セメントプラントの操業条件、集塵ダストの処
理条件、水銀除去装置の形式を表２に示す。また、図１
のシステムを用いなかった他は同一の条件で処理した場
合のセメントプラント排ガス中の水銀濃度を比較例とし
て表２に示した。Embodiment 9 The dust collected in the cement production test plant is led to the system shown in FIG. 1 to remove the mercury by heating, and the dust collected from the mercury is returned to the cement plant again. Cement was produced under normal conditions. The amount of mercury in the cement raw material and the amount of waste added were adjusted to obtain the values shown in Table 2. Table 2 shows the operating conditions of the cement plant, the conditions for treating dust collection, and the type of mercury removal device. FIG.
Table 2 shows the mercury concentration in the exhaust gas of the cement plant when treated under the same conditions except that the system was not used.
【００２２】[0022]
【表２】 [Table 2]
【００２３】表１に示すように、本発明の処理方法によ
れば、集塵ダストから水銀を極めて低濃度になるまで除
去することができ、さらに集塵ダストを加熱処理した排
ガス中の水銀量も極めて低濃度に抑制することができ
た。また、セメント製造テストプラントでの実施例９に
示したように、本発明の処理方法を使用した場合には、
使用しなかった場合に比べて、セメント製造テストプラ
ント排ガス中の水銀濃度を格段に低減することができ
た。As shown in Table 1, according to the treatment method of the present invention, mercury can be removed from the collected dust until the concentration becomes extremely low, and the amount of mercury in the exhaust gas obtained by heat-treating the collected dust. Was also suppressed to an extremely low concentration. Further, as shown in Example 9 in a cement production test plant, when the treatment method of the present invention was used,
The mercury concentration in the exhaust gas from the cement manufacturing test plant was significantly reduced as compared with the case where no cement was used.
【００２４】〔実施例１０〕セメント製造工場で捕集し
た集塵ダスト１００ｇを両端が開口した試験管(20mmφ
×700mm)の中央部に充填し、２００〜５００℃で３０分
間加熱した。このとき試験管の片側開口部から空気を１
００ml/分導入し、他端から排出されたガスを冷却管に
導いて室温まで冷却した。集塵ダストに含まれる水銀の
含有量と処理効果を表３に示した。Example 10 A test tube (20 mmφ) having 100 g of dust collected at a cement manufacturing plant was opened at both ends.
(* 700 mm) and heated at 200 to 500 ° C for 30 minutes. At this time, air was released from one side opening of the test tube.
At a rate of 00 ml / min, the gas discharged from the other end was led to a cooling tube and cooled to room temperature. Table 3 shows the mercury content and the treatment effect of the dust collected.
【００２５】[0025]
【表３】 [Table 3]
【００２６】〔実施例１１〕セメント製造工程の排ガス
路に設置した電気集塵機によって捕集した集塵ダストの
一部を加熱炉に供給して所定温度に加熱し、その加熱ガ
スを冷却部に導入して冷却してガス中の水銀を分離し
た。冷却したガスは吸引ファンを通じて再び排ガス路に
戻した。この処理結果を表４に示した。[Embodiment 11] Part of the dust collected by an electric dust collector installed in an exhaust gas passage of a cement manufacturing process is supplied to a heating furnace and heated to a predetermined temperature, and the heated gas is introduced into a cooling unit. And cooled to separate mercury in the gas. The cooled gas was returned to the exhaust gas path again through the suction fan. Table 4 shows the processing results.
【００２７】[0027]
【表４】 [Table 4]
【００２８】[0028]
【発明の効果】セメント製造工程から排出された水銀等
の揮発性金属成分は集塵ダストに高濃度に濃縮するの
で、本発明の処理方法によればこの集塵ダストを処理す
ることによって排ガス中に含まれる水銀等を効率よく除
去することができる。また、本発明の方法は集塵ダスト
を処理するので、大掛かりな設備を必要とせず、既存の
排ガス設備に付設するだけで容易に実施することができ
る。さらに、本発明は乾式の処理方法であるので、水銀
等を除去した排ガスを再びセメント排ガス路に戻して排
出することができ、個別の排ガス設備を設ける必要がな
い。As described above, the volatile metal components such as mercury discharged from the cement manufacturing process are concentrated in the dust collected at a high concentration. Can be efficiently removed. Further, since the method of the present invention treats dust collection dust, it does not require a large-scale facility, and can be easily implemented simply by attaching it to an existing exhaust gas facility. Further, since the present invention is a dry treatment method, the exhaust gas from which mercury and the like have been removed can be returned to the cement exhaust gas path and discharged again, and there is no need to provide a separate exhaust gas facility.
【図１】 本発明の処理工程を示すフロー図FIG. 1 is a flowchart showing the processing steps of the present invention.
１０−排ガス路、２１−集塵機、２２−煙突、３０−加
熱炉、３１−水銀除去手段、３２−吸引ファン10-exhaust gas path, 21-dust collector, 22-chimney, 30-heating furnace, 31-mercury removing means, 32-suction fan
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ テーマコート゛(参考） Ｃ０４Ｂ 7/60 Ｂ０１Ｄ 53/34 ＺＡＢ (72)発明者 山口 修 千葉県佐倉市大作二丁目４番２号 太平洋 セメント株式会社中央研究所内 (72)発明者 吉岡 勇治 岩手県大船渡市赤崎町字跡浜21−６ 太平 洋セメント株式会社大船渡工場内 Ｆターム(参考） 4D002 AA29 AC05 BA02 BA03 BA04 BA12 BA13 CA07 DA15 DA21 DA25 DA26 DA35 DA41 EA02 EA05 FA10 HA08 4G066 AA02B AA05B AA45B AA46B BA07 CA47 DA02 ──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. 7 Identification FI FI Theme Court ゛ (Reference) C04B 7/60 B01D 53/34 ZAB (72) Inventor Osamu Yamaguchi 2-4-2 Daisaku, Sakura City, Chiba Prefecture Taiheiyo Cement Co., Ltd. Central Research Laboratory (72) Inventor Yuji Yoshioka 21-6 Atohama, Akasaki-cho, Ofunato-shi, Iwate Prefecture Taiheiyo Cement Co., Ltd. Ofunato Plant F-term (reference) 4D002 AA29 AC05 BA02 BA03 BA04 BA12 BA13 CA07 DA15 DA21 DA25 DA26 DA35 DA41 EA02 EA05 FA10 HA08 4G066 AA02B AA05B AA45B AA46B BA07 CA47 DA02
Claims (8)
集塵ダストを加熱炉に導き、集塵ダストに含まれる揮発
性金属成分の揮発温度以上に加熱して上記揮発性金属成
分をガス化して除去し、揮発性金属成分を除去した集塵
ダストをセメント原料の一部に用いることを特徴とする
セメント製造排ガスの処理方法。1. Dust-collected dust collected from an exhaust gas of a cement production process is led to a heating furnace, and heated to a temperature equal to or higher than a volatile temperature of a volatile metal component contained in the dust-collected dust to gasify the volatile metal component. A method for treating exhaust gas from cement production, comprising using dust collected from the volatile matter component after removing the volatile metal component as a part of a cement raw material.
を含む排ガスを水銀除去装置に導いて排ガスから水銀を
除去する請求項１に記載する排ガスの処理方法。2. The method for treating exhaust gas according to claim 1, wherein the volatile metal component is mercury, and the exhaust gas containing mercury vapor is guided to a mercury removing device to remove mercury from the exhaust gas.
溶液ないし酸化性溶液に水銀を吸収させる方法である請
求項２に記載する排ガスの処理方法。3. The method for treating exhaust gas according to claim 2, wherein the method of removing mercury from the exhaust gas is a method of absorbing mercury into an acidic solution or an oxidizing solution.
または金属硫化物による吸着除去である請求項２に記載
する排ガスの処理方法4. The method for treating exhaust gas according to claim 2, wherein the method for removing mercury from the exhaust gas is adsorption removal using sulfur or metal sulfide.
炭または活性炭を担持した吸着媒体による吸着除去であ
る請求項２に記載する排ガスの処理方法。5. The method for treating exhaust gas according to claim 2, wherein the method for removing mercury from the exhaust gas is adsorption removal using activated carbon or an adsorption medium supporting activated carbon.
と反応する金属または水銀と反応する金属を担持した吸
着媒体による吸着除去である請求項２に記載する排ガス
の処理方法。6. The method for treating exhaust gas according to claim 2, wherein the method for removing mercury from exhaust gas is adsorption removal using an adsorption medium carrying a metal that reacts with mercury or a metal that reacts with mercury.
却部に導いて揮発性金属成分の析出温度以下に冷却し、
これを液化ないし固化してガス中から分離することによ
って排ガス中の揮発性金属成分の濃度を低減する請求項
１に記載する排ガスの処理方法。7. A high-temperature gas containing a gasified metal component is guided to a cooling unit, and cooled to a temperature lower than a deposition temperature of a volatile metal component.
2. The exhaust gas treatment method according to claim 1, wherein the concentration of volatile metal components in the exhaust gas is reduced by liquefying or solidifying and separating the gas from the gas.
排ガスによって加熱炉を加熱する請求項１〜７の何れか
に記載する排ガスの処理方法。8. The method for treating exhaust gas according to claim 1, wherein the heating furnace is heated by the hot exhaust gas discharged in the cement production process.
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|---|---|---|---|
| JP2001392854A JP2002355531A (en) | 2001-03-27 | 2001-12-25 | Method of treating exhaust gas in cement production |
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|---|---|---|---|
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Cited By (45)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005005025A1 (en) * | 2003-07-10 | 2005-01-20 | Taiheiyo Cement Corporation | Device and method for processing combustion exhaust gas |
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