JPH11104439A - Removing agent for acidic ingredient in gas and removal of acidic ingredient - Google Patents
Removing agent for acidic ingredient in gas and removal of acidic ingredientInfo
- Publication number
- JPH11104439A JPH11104439A JP9268956A JP26895697A JPH11104439A JP H11104439 A JPH11104439 A JP H11104439A JP 9268956 A JP9268956 A JP 9268956A JP 26895697 A JP26895697 A JP 26895697A JP H11104439 A JPH11104439 A JP H11104439A
- Authority
- JP
- Japan
- Prior art keywords
- gas
- removing agent
- acidic
- acidic component
- carbonate
- 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.)
- Granted
Links
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、気体中の酸性成分
除去剤および酸性成分除去方法に関する。The present invention relates to an agent for removing acidic components in a gas and a method for removing acidic components.
【０００２】[0002]
【従来の技術】ゴミ焼却炉などから排出されるダイオキ
シンの除去方法として、一般にダイオキシンの発生に関
与するとされている塩酸を中和、吸収するために、消石
灰を酸性成分除去剤として用いることが知られている。
この場合、焼却炉等からの排ガス排出路における１５０
〜２５０℃の温度域に消石灰を分散し、バグフィルタで
捕集し、ろ過層を形成して酸性成分を除去している。2. Description of the Related Art As a method of removing dioxin discharged from a garbage incinerator or the like, it is known that slaked lime is used as an acidic component remover in order to neutralize and absorb hydrochloric acid which is generally involved in the generation of dioxin. Have been.
In this case, 150 mm in the exhaust gas discharge passage from the incinerator etc.
Slaked lime is dispersed in a temperature range of ~ 250 ° C, collected by a bag filter, and a filtration layer is formed to remove acidic components.
【０００３】[0003]
【発明が解決しようとする課題】しかし消石灰は、反応
当量に対して過剰に使用する必要がある、高温では除去
性能が低下する、廃棄するダスト量が増加するなどの欠
点があった。本発明は、高温の排ガスからも効率良く、
塩酸などの酸性成分を吸着除去でき、かつ廃棄処理も容
易な酸性成分除去剤を提供することを目的とする。However, slaked lime has disadvantages such as the necessity of using it in excess of the reaction equivalent, the removal performance being reduced at high temperatures, and the amount of dust to be discarded being increased. The present invention is efficient even from high temperature exhaust gas,
An object of the present invention is to provide an acidic component remover capable of adsorbing and removing acidic components such as hydrochloric acid and easily disposing.
【０００４】[0004]
【課題を解決するための手段】本発明の第１の態様は、
重量基準の平均粒子径が２０μｍ以下の粒子であって、
水銀圧入式細孔分布測定装置で測定した細孔直径１０〜
１０００ｎｍの細孔容積が０．２ｃｃ／ｇ以上の、炭酸
ナトリウムまたは炭酸カリウムからなる気体中の酸性成
分除去剤である。According to a first aspect of the present invention, there is provided:
Particles having a weight-based average particle size of 20 μm or less,
Pore diameter 10 measured with a mercury intrusion-type pore distribution measuring device
It is an acidic component removing agent in a gas composed of sodium carbonate or potassium carbonate having a pore volume of 1000 nm of 0.2 cc / g or more.
【０００５】この酸性成分除去剤は、炭酸ナトリウムま
たは炭酸カリウムからなるため、高温の排ガス中で、酸
性成分を吸着する能力が高い。炭酸ナトリウムと炭酸カ
リウムの混合物であってもよい。[0005] Since this acidic component remover is made of sodium carbonate or potassium carbonate, it has a high ability to adsorb acidic components in high-temperature exhaust gas. It may be a mixture of sodium carbonate and potassium carbonate.
【０００６】平均粒子径は、重量基準で２０μｍ以下で
あることが必要である。なお、本明細書では、平均粒子
径はすべて重量基準で表す。平均粒子径が、２０μｍを
超える場合は、酸性成分の除去効率が落ちるので好まし
くない。特に好ましい平均粒子径は、１〜１５μｍであ
る。It is necessary that the average particle size is not more than 20 μm on a weight basis. In this specification, all the average particle diameters are expressed on a weight basis. If the average particle diameter exceeds 20 μm, the efficiency of removing acidic components is reduced, which is not preferable. A particularly preferred average particle size is 1 to 15 μm.
【０００７】細孔容積は、水銀圧入式細孔分布測定装置
で測定した細孔容積が０．２ｃｃ／ｇ以上であることが
必要である。本明細書では、細孔容積はすべて水銀圧入
式細孔分布測定装置で測定したものである。この細孔容
積は、細孔直径で１０〜１０００ｎｍの細孔の細孔容積
である。細孔容積が０．２ｃｃ／ｇに満たない場合は、
酸性成分の除去効率が落ちるので好ましくない。特に好
ましい、細孔直径で１０〜１０００ｎｍの細孔の細孔容
積は、０．３ｃｃ／ｇ以上である。第１の態様の酸性成
分除去剤は、ＢＥＴ法で測定した比表面積が４ｍ2 ／ｇ
以上である場合は、さらに好ましい。The pore volume needs to be 0.2 cc / g or more as measured by a mercury intrusion-type pore distribution measuring device. In this specification, all pore volumes are measured by a mercury intrusion-type pore distribution measuring device. This pore volume is a pore volume of pores having a pore diameter of 10 to 1000 nm. If the pore volume is less than 0.2 cc / g,
It is not preferable because the efficiency of removing acidic components is reduced. Particularly preferred pore volume of pores having a pore diameter of 10 to 1000 nm is 0.3 cc / g or more. The acidic component remover of the first embodiment has a specific surface area of 4 m 2 / g measured by the BET method.
The above case is more preferable.
【０００８】炭酸水素ナトリウムまたは炭酸水素カリウ
ムは、高温の排ガス中に投入したときに、容易に炭酸ナ
トリウムまたは炭酸カリウムに転換する。このときの炭
酸ナトリウムまたは炭酸カリウムが上記第１の態様の酸
性成分除去剤の物性を満たす場合は、同様に高い酸性成
分除去性を有する。[0008] Sodium bicarbonate or potassium bicarbonate readily converts to sodium carbonate or potassium carbonate when injected into hot exhaust gas. When the sodium carbonate or potassium carbonate at this time satisfies the physical properties of the acidic component remover of the first embodiment, it also has high acidic component removeability.
【０００９】したがって、本発明は第２の態様として、
重量基準の平均粒子径が２０μｍ以下の粒子であって、
細孔直径１０ｎｍ〜１０μｍの細孔の細孔容積が０．１
ｃｃ／ｇ以上の、炭酸水素ナトリウムまたは炭酸水素カ
リウムからなる気体中の酸性成分除去剤を提供する。こ
の物性の炭酸水素ナトリウムまたは炭酸水素カリウム
は、高温の排ガス中に投入したときに、本発明の第１の
態様の酸性成分除去剤に容易に転換する。炭酸水素ナト
リウムおよび炭酸水素カリウムを混合して使用すること
もできる。第２の態様の酸性成分除去剤は、ＢＥＴ法で
測定した比表面積が２ｍ2 ／ｇ以上である場合は、さら
に好ましい。Therefore, the present invention provides, as a second aspect,
Particles having a weight-based average particle size of 20 μm or less,
The pore volume of pores having a pore diameter of 10 nm to 10 μm is 0.1
An agent for removing acidic components in a gas consisting of sodium hydrogen carbonate or potassium hydrogen carbonate of cc / g or more. This physical property of sodium hydrogen carbonate or potassium bicarbonate is easily converted to the acidic component-removing agent of the first aspect of the present invention when injected into a high-temperature exhaust gas. It is also possible to use a mixture of sodium hydrogen carbonate and potassium hydrogen carbonate. The acidic component remover of the second embodiment is more preferably when the specific surface area measured by the BET method is 2 m 2 / g or more.
【００１０】本発明の、酸性成分除去剤は、処理すべき
気体中に分散し、気体中の酸性成分の少なくとも一部を
吸着した酸性成分除去剤を、バグフィルタで捕集するこ
とにより、気体中の酸性成分を除去できる。第２の態様
の酸性成分除去剤を用いる場合は、炭酸水素ナトリウム
または炭酸水素カリウムが、炭酸ナトリウムまたは炭酸
カリウムに速やかに転換するよう、２００〜３００℃の
気体中に分散するのが好ましい。The acidic component-removing agent of the present invention is dispersed in a gas to be treated, and the acidic component-removing agent adsorbing at least a part of the acidic component in the gas is collected by a bag filter. It can remove acidic components in it. When the acidic component removing agent of the second embodiment is used, it is preferable that sodium bicarbonate or potassium bicarbonate is dispersed in a gas at 200 to 300 ° C. so as to be rapidly converted to sodium carbonate or potassium carbonate.
【００１１】[0011]
【発明の実施の形態】本発明の第１の態様の酸性成分除
去剤を製造するには、通常の炭酸水素ナトリウムまたは
炭酸水素カリウムを粉砕などによって粒径２０μｍ以下
にし、さらに熱処理を行って炭酸ナトリウムに転換する
のが好ましい。このときの熱処理条件としては、２００
〜４００℃で保持するのが好ましい。熱処理前の、炭酸
水素ナトリウムまたは炭酸水素カリウムは、そのまま本
発明の第２の態様の酸性成分除去剤として使用できる。BEST MODE FOR CARRYING OUT THE INVENTION In order to produce the acidic component-removing agent according to the first aspect of the present invention, ordinary sodium bicarbonate or potassium bicarbonate is reduced to a particle size of 20 μm or less by milling or the like, and further subjected to a heat treatment. Conversion to sodium is preferred. The heat treatment conditions at this time were 200
It is preferable to keep the temperature at 400 ° C. Sodium bicarbonate or potassium bicarbonate before heat treatment can be used as it is as the acidic component remover of the second embodiment of the present invention.
【００１２】本発明の酸性成分除去剤を使用するにあた
っては、酸性成分除去剤を気体中に分散し、バグフィル
タで捕集すると、バグフィルタ表面に酸性成分除去剤の
ろ過層が形成されるので、効率的に酸性成分を除去でき
る。When the acidic component remover of the present invention is used, the acidic component remover is dispersed in a gas and collected by a bag filter, so that a filtration layer of the acidic component remover is formed on the surface of the bag filter. It is possible to efficiently remove acidic components.
【００１３】また、微細な炭酸ナトリウム、炭酸カリウ
ム、炭酸水素ナトリウム、炭酸水素カリウムは、長期間
保存しておいた場合に固結してしまう場合がある。本発
明の酸性成分除去剤は、固結によってその特性を低下さ
せるおそれがあるので、固結防止剤を含有するのが好ま
しい。固結防止剤としてはシリカが好ましい。具体的に
は、ヒュームドシリカと呼ばれる微細な無水ケイ酸が好
ましい。その含有量としては、酸性成分除去剤の０．１
〜１重量％程度が好ましい。Further, fine sodium carbonate, potassium carbonate, sodium hydrogencarbonate, and potassium hydrogencarbonate may solidify when stored for a long period of time. The acidic component-removing agent of the present invention preferably contains an anti-caking agent since its properties may be reduced by caking. Silica is preferred as the anti-caking agent. Specifically, fine silicic anhydride called fumed silica is preferable. Its content is 0.1% of the acidic component remover.
About 1% by weight is preferred.
【００１４】[0014]
「例１」旭硝子株式会社製の平均粒子径８５μｍの炭酸
水素ナトリウムを、気流による分級機を備えた衝撃式乾
式粉砕機（ホソカワミクロン株式会社製、商品名ＡＣＭ
パルベライザー）にて微粉砕して、平均粒子径３．９μ
ｍの炭酸水素ナトリウムを得た。この炭酸水素ナトリウ
ムの細孔直径１０ｎｍ〜１０μｍの細孔容積は０．７１
４ｃｃ／ｇであった。ＢＥＴ法で測定した比表面積は
３．３１ｍ2 ／ｇであった。"Example 1" An impact-type dry pulverizer (trade name: ACM, manufactured by Hosokawa Micron Co., Ltd.) equipped with a classifier by air flow was prepared by using sodium hydrogen carbonate having an average particle diameter of 85 μm manufactured by Asahi Glass Co., Ltd.
(Pulverizer) to give an average particle size of 3.9μ
m of sodium bicarbonate were obtained. The pore volume of this sodium hydrogencarbonate having a pore diameter of 10 nm to 10 μm is 0.71.
It was 4 cc / g. The specific surface area measured by the BET method was 3.31 m 2 / g.
【００１５】この炭酸水素ナトリウムを、２００℃の恒
温乾燥器内に３時間静置して、炭酸ナトリウムとした。
この炭酸ナトリウムは、平均粒子径が３．９μｍで、細
孔直径１０〜１０００ｎｍの細孔容積は０．３７８ｃｃ
／ｇであった。平均粒子径はリーズ・アンド・ノースロ
ップ社製マイクロトラック９３２０ＨＲＡを用い、細孔
容積はマイクロメリティックス社製ポアサイザ９３１０
を用いて、それぞれ測定した。この酸性成分除去剤は、
ＢＥＴ法で測定した比表面積が６．１４ｍ2 ／ｇであっ
た。The sodium hydrogen carbonate was left in a constant-temperature oven at 200 ° C. for 3 hours to obtain sodium carbonate.
This sodium carbonate has an average particle diameter of 3.9 μm, a pore volume of 10 to 1000 nm and a pore volume of 0.378 cc.
/ G. The average particle size was measured using Microtrac 9320HRA manufactured by Leeds & Northrop Co., and the pore volume was controlled by Micromeritics Co.
Was measured using the method described above. This acidic component remover
The specific surface area measured by the BET method was 6.14 m 2 / g.
【００１６】この炭酸ナトリウムに固結防止剤として、
平均粒子径０．０１μｍのヒュームドシリカ（株式会社
トクヤマ製、商品名レオシールＣＰ−１０２）を０．５
重量％添加して混合した。As an anti-caking agent for this sodium carbonate,
0.5 μm of fumed silica having an average particle diameter of 0.01 μm (trade name: Leoseal CP-102, manufactured by Tokuyama Corporation)
% By weight and mixed.
【００１７】このようにして得られた酸性成分除去剤に
ついて、酸性ガスの吸収性能を次のようにして評価し
た。縦に保持したポリ塩化ビニル製パイプに試料を入
れ、両端を濾布で封じた。このパイプの下部から上部に
向かって、濾布を通して濃度６００体積ｐｐｍの塩酸を
含む空気を流した。流した塩酸の総量は、試料の炭酸ナ
トリウムの理論反応量の半分、ガス速度は１ｍ／秒とし
た。充填した炭酸ナトリウムを１規定の塩酸で中和滴定
して未反応量を求めることにより算出した塩酸の吸収率
は、２０％であった。また、この酸性成分除去剤は、室
内に６０日間放置した後でも、良好な流動性を有してい
た。The acidic component removing agent thus obtained was evaluated for its ability to absorb acidic gas as follows. The sample was placed in a polyvinyl chloride pipe held vertically, and both ends were sealed with a filter cloth. Air containing hydrochloric acid having a concentration of 600 ppm by volume was passed through the filter cloth from the bottom to the top of the pipe. The total amount of the flowed hydrochloric acid was half the theoretical reaction amount of sodium carbonate in the sample, and the gas velocity was 1 m / sec. The absorption rate of hydrochloric acid calculated by neutralizing and titrating the filled sodium carbonate with 1N hydrochloric acid to determine the unreacted amount was 20%. The acidic component remover had good fluidity even after being left indoors for 60 days.
【００１８】「例２（比較例）」旭硝子株式会社製の平
均粒子径８５μｍの炭酸水素ナトリウムを、高速で回転
するピンと粒子との衝撃によって粉砕するピンミル式粉
砕機（ホソカワミクロン株式会社社製、商品名コロプレ
ックス）にて粉砕することによって、平均粒子径５１μ
ｍの炭酸水素ナトリウムを得た。この炭酸水素ナトリウ
ムを、２００℃の恒温乾燥器内で３時間静置し、炭酸ナ
トリウムとした。Example 2 (Comparative Example) A pin mill type pulverizer (manufactured by Hosokawa Micron Co., Ltd., manufactured by Asahi Glass Co., Ltd.) for pulverizing sodium bicarbonate having an average particle diameter of 85 μm by the impact of high-speed rotating pins and particles. Pulverized by the name Coroplex) to give an average particle size of 51μ.
m of sodium bicarbonate were obtained. This sodium hydrogencarbonate was allowed to stand in a constant-temperature oven at 200 ° C. for 3 hours to obtain sodium carbonate.
【００１９】例１と同様に評価したところ、平均粒子径
が５１μｍで、水銀圧入式細孔分布測定装置で測定した
細孔直径１０〜１０００ｎｍの細孔容積は、０．２９３
ｃｃ／ｇであった。塩酸ガスの吸収率は、１０％であっ
た。例１に比べて、平均粒子径が大きいことが、低い吸
収率の原因であると思われる。When evaluated in the same manner as in Example 1, the average particle diameter was 51 μm, and the pore volume with a pore diameter of 10 to 1000 nm measured by a mercury intrusion-type pore distribution measuring apparatus was 0.293.
cc / g. The absorption rate of hydrochloric acid gas was 10%. Larger average particle size than in Example 1 seems to be responsible for the lower absorption.
【００２０】「例３（比較例）」旭硝子株式会社製の平
均粒子径２５μｍの炭酸ナトリウム（粒灰；炭酸水素ナ
トリウムを熱処理して得た炭酸ナトリウムを１水塩にし
た後、再度無水塩としたもの）を、気流による分級機を
備えた衝撃式乾式粉砕機（ホソカワミクロン株式会社
製、商品名ＡＣＭパルベライザー）で微粉砕することに
よって、平均粒子径１０μｍの炭酸ナトリウムを得た。Example 3 (Comparative Example) Sodium carbonate having an average particle size of 25 μm manufactured by Asahi Glass Co., Ltd. (grain ash; sodium carbonate obtained by heat-treating sodium hydrogencarbonate was converted into monohydrate, and then dried again with anhydrous salt. This was finely pulverized with an impact-type dry pulverizer (manufactured by Hosokawa Micron Corporation, trade name: ACM Pulverizer) equipped with an airflow classifier to obtain sodium carbonate having an average particle diameter of 10 μm.
【００２１】例１と同様に評価したところ、平均粒子径
が３．４μｍで、水銀圧入式細孔分布測定装置で測定し
た細孔直径１０〜１０００ｎｍの細孔容積は、０．０８
８ｃｃ／ｇであった。塩酸の吸収率は、４％であった。
例１に比べて、細孔直径１０〜１０００ｎｍの細孔容積
が小さいことが、低い吸収率の原因であると思われる。When evaluated in the same manner as in Example 1, the average particle diameter was 3.4 μm, and the pore volume with a pore diameter of 10 to 1000 nm measured by a mercury intrusion type pore distribution measuring apparatus was 0.08.
It was 8 cc / g. The hydrochloric acid absorption was 4%.
Compared to Example 1, the small pore volume with a pore diameter of 10 to 1000 nm seems to be responsible for the low absorption.
【００２２】[0022]
【発明の効果】本発明の酸性成分除去剤は、排ガス中の
酸性成分、特に塩酸成分を高い効率で吸収できる。ま
た、炭酸ナトリウムは水溶性であるので、排ガス中の酸
性成分除去後のダストは、水洗処理できるという優れた
効果も有する。The acidic component remover of the present invention can absorb acidic components, particularly hydrochloric acid components, in exhaust gas with high efficiency. In addition, since sodium carbonate is water-soluble, the dust after removing the acidic components in the exhaust gas has an excellent effect that it can be washed with water.
【００２３】本発明の酸性成分除去剤は、ゴミ焼却場な
どから排出される排ガス中の酸性成分、特に塩酸を効率
良く除去し、また発生する焼却残さを減少できるなどの
効果を有し、環境への影響を大幅に低減できる。The acidic component remover of the present invention has an effect of efficiently removing acidic components, particularly hydrochloric acid, in exhaust gas discharged from a garbage incineration plant and the like, and has the effect of reducing incineration residues generated. Impact can be greatly reduced.
Claims (7)
子であって、水銀圧入式細孔分布測定装置で測定した細
孔直径１０〜１０００ｎｍの細孔容積が０．２ｃｃ／ｇ
以上の、炭酸ナトリウムまたは炭酸カリウムからなる気
体中の酸性成分除去剤。1. A particle having a weight-based average particle diameter of 20 μm or less and having a pore volume of 0.2 cc / g having a pore diameter of 10 to 1000 nm measured by a mercury intrusion-type pore distribution measuring device.
The above-mentioned acidic component removing agent in a gas comprising sodium carbonate or potassium carbonate.
以上である請求項１記載の酸性成分除去剤。2. The specific surface area measured by the BET method is 4 m 2 / g.
The acidic component-removing agent according to claim 1, which is as described above.
子であって、水銀圧入式細孔分布測定装置で測定した細
孔直径１０ｎｍ〜１０μｍの細孔容積が０．１ｃｃ／ｇ
以上の、炭酸水素ナトリウムまたは炭酸水素カリウムか
らなる気体中の酸性成分除去剤。3. Particles having a weight-based average particle diameter of 20 μm or less and having a pore volume of 0.1 cc / g having a pore diameter of 10 nm to 10 μm measured by a mercury intrusion-type pore distribution measuring apparatus.
The above-mentioned acidic component removing agent in a gas comprising sodium hydrogen carbonate or potassium hydrogen carbonate.
以上である請求項３記載の酸性成分除去剤。4. The specific surface area measured by the BET method is 2 m 2 / g.
The acidic component remover according to claim 3, which is the above.
たは４記載の酸性成分除去剤。5. The acidic component-removing agent according to claim 1, further comprising an anti-caking agent.
酸性成分除去剤。6. The acidic component-removing agent according to claim 5, wherein the anti-caking agent is silica.
酸性成分除去剤を、処理すべき気体中に分散し、バグフ
ィルタで捕集する、気体中の酸性成分除去方法。7. A method for removing an acidic component in a gas, comprising dispersing the acidic component-removing agent according to claim 1, 2, 3, 4, 5 or 6 in a gas to be treated and collecting it with a bag filter.
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