JP2006026520A - Method for removing mercury in exhaust gas - Google Patents
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- JP2006026520A JP2006026520A JP2004208447A JP2004208447A JP2006026520A JP 2006026520 A JP2006026520 A JP 2006026520A JP 2004208447 A JP2004208447 A JP 2004208447A JP 2004208447 A JP2004208447 A JP 2004208447A JP 2006026520 A JP2006026520 A JP 2006026520A
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Abstract
Description
本発明は焼却炉等の高温排ガス中に含まれる水銀を除去する方法に関する。 The present invention relates to a method for removing mercury contained in high-temperature exhaust gas such as an incinerator.
従来の高温排ガス中の水銀除去方法は炭素質吸着剤と排ガスを接触させる方法、排ガスをNa2S水溶液やNaHS水溶液と接触させる方法や洗煙排水を砂ろ過塔、キレート樹脂塔に通す方法等があった。 Conventional methods for removing mercury in high-temperature exhaust gas include contacting carbonaceous adsorbent with exhaust gas, contacting exhaust gas with Na 2 S aqueous solution or NaHS aqueous solution, passing smoke-washed wastewater through sand filtration tower, chelate resin tower, etc. was there.
また、活性炭に-SH基を有するキレート剤を吸着させたキレート吸着活性炭に水銀ガスを接触させ水銀を除去する技術も公知である（特公昭４８−５４３６）。しかし、この方法では室温付近の水銀含有ガスしか処理できず、60℃以上の高温ガスの処理は不可能であり、処理する場合は室温付近まで排ガスを冷却する必要があり、冷却コストが大きく実用的に問題があった。しかも-SH基を有するキレートを活性炭に吸着させた場合、-SH基が酸素により酸化されて発熱するため冷却を必要とした。またその酸性度により装置の腐食対策が必要であり、経済的でなかった。 A technique for removing mercury by bringing mercury gas into contact with a chelate-adsorbed activated carbon obtained by adsorbing a chelating agent having a —SH group on activated carbon is also known (Japanese Patent Publication No. 48-5436). However, this method can only process mercury-containing gas near room temperature, and it is impossible to process high-temperature gas at 60 ° C or higher. When processing, it is necessary to cool the exhaust gas to near room temperature. There was a problem. In addition, when a chelate having a —SH group is adsorbed on activated carbon, the —SH group is oxidized by oxygen and generates heat, and thus cooling is required. Moreover, due to its acidity, it was necessary to take measures against corrosion of the equipment, which was not economical.
更に、ごみ焼却排ガス中にジチオカルバミン酸塩の水溶液を噴霧し水銀含有ダストを回収する方法が知られているが、水銀除去能力に問題がある。（特開平５−２０８１１７）
以上のように高温排ガス中の水銀を除去する方法はいろいろ提案されているが、水銀除去能力が小さいことや操作が煩雑で費用がかかる等の問題点があった。 As described above, various methods for removing mercury from the high-temperature exhaust gas have been proposed, but there are problems such as low mercury removal capability and complicated and expensive operations.
本発明者らは、上記問題を解決するために鋭意検討した結果、新規で経済性のある方法を見出し、本発明を完成するに至った。 As a result of diligent studies to solve the above problems, the present inventors have found a new and economical method and have completed the present invention.
すなわち本発明は、水銀とキレートを形成し得るキレート剤が活性炭に吸着されてなる吸着剤に、水銀を含有する高温排ガスを接触させて水銀を吸着除去する方法において、吸着剤の含有水分量を、水銀吸着に必な量以上に維持しながら行なうことを特徴とする水銀除去方法に関する。 That is, the present invention relates to a method for adsorbing and removing mercury by contacting a high-temperature exhaust gas containing mercury with an adsorbent obtained by adsorbing a chelating agent capable of forming a chelate with mercury on activated carbon. The present invention also relates to a mercury removal method characterized in that it is carried out while maintaining the amount more than necessary for mercury adsorption.
前記、キレート剤としては式（１）で表される基（以下-CS-SM基とも称する）を含むキレート剤が好ましい。
前記、式（１）で表される基-を含むキレート剤としては、式（２）で表されるピペリジンジチオカルバミン酸化合物、式（３）で表されるチオモルホリンジチオカルバミン酸化合物または式（４）で表される1,4-ピペラジンジカルボジチエート化合物から選ばれる化合物であることが好ましい。 Examples of the chelating agent containing a group represented by the formula (1) include a piperidine dithiocarbamic acid compound represented by the formula (2), a thiomorpholine dithiocarbamic acid compound represented by the formula (3), or the formula (4). A compound selected from 1,4-piperazine dicarbodithiate compounds represented by the formula:
本発明によれば充填塔に高温排ガスを通過させるだけで、高温排ガス中の水銀を簡単に効率良く除去することが可能であり、煩雑で費用がかかる操作をする必要がなく経済的メリットが大変大きい。 According to the present invention, it is possible to easily and efficiently remove mercury in the high temperature exhaust gas simply by passing the high temperature exhaust gas through the packed tower, and it is not necessary to perform a complicated and expensive operation, resulting in a great economic advantage. large.
本発明を実施するための吸着剤は、水銀とキレートを形成し得るキレート剤を吸着させた活性炭であれば特に限定されないが、好ましくは-CS-SM基を含むキレート剤を活性炭に吸着させたものが良い。 The adsorbent for carrying out the present invention is not particularly limited as long as it is activated carbon on which a chelating agent capable of forming a chelate with mercury is adsorbed, but preferably a chelating agent containing a -CS-SM group is adsorbed on the activated carbon. Things are good.
-CS-SM基を含むキレート剤は特に限定されないが、例えば、前記式（２）で表されるピペリジンジチオカルバミン酸化合物、前記式（３）で表されるチオモルホリンジチオカルバミン酸化合物、前記式（４）で表される1,4-ピペラジンジカルボジチエート化合物が挙げられる。これらの化合物は150℃までの高温ガス中で安定であり、高温での水銀ガスとのキレート反応に好都合な化合物である。 The chelating agent containing a -CS-SM group is not particularly limited. For example, the piperidine dithiocarbamic acid compound represented by the formula (2), the thiomorpholine dithiocarbamic acid compound represented by the formula (3), the formula (4) 1,4-piperazine dicarbodithiate compounds represented by: These compounds are stable in high-temperature gas up to 150 ° C. and are favorable for chelation reaction with mercury gas at high temperature.
本発明者らは-CS-SM基を含むキレート剤は150℃以下の温度において有毒な二硫化炭素ガスを生成することがなく、安定であることに着目し、また活性炭に吸着させた-CS-SM基を含むキレート剤が安定に作用するためには、すでに吸着されている水分が必要であることを見出し、本発明を完成させたものである。 The present inventors focused on the fact that a chelating agent containing a -CS-SM group does not generate toxic carbon disulfide gas at a temperature of 150 ° C. or lower and is stable, and also has -CS adsorbed on activated carbon. The present inventors have found that in order for a chelating agent containing a -SM group to act stably, water that has already been adsorbed is necessary, and the present invention has been completed.
すなわち、活性炭に吸着したキレート剤には水分子が付いており、キレート剤が液体キレートと同様に水銀キレートを生成するには、キレートに配位している水分子の存在が不可欠である。この理由について本発明者等はキレート剤を吸着した活性炭には通常水分が4〜8重量%含まれているが、高温に曝されキレート剤に配位する水分子が無くなれば、キレート剤は活性炭中で結晶析出してしまい、液体キレートと同様な機能を果たすことができなくなってしまうからではないかと考えている。 That is, water molecules are attached to the chelating agent adsorbed on the activated carbon, and the presence of water molecules coordinated to the chelate is indispensable for the chelating agent to produce mercury chelate as well as liquid chelate. For this reason, the present inventors have generally found that the activated carbon adsorbed with the chelating agent usually contains 4 to 8% by weight of water, but if the water molecule that is coordinated to the chelating agent disappears when exposed to high temperature, the chelating agent is activated carbon. It is thought that it is because the crystal is precipitated in the inside and the function similar to the liquid chelate cannot be performed.
従って、水銀を含む高温排ガスをキレート吸着した活性炭と接触させる場合、活性炭中に含まれている水分が失われないように補給する必要があり、排ガス中に必要な量の水分が含まれていない場合は強制的に補給することが必要となる。 Therefore, when high temperature exhaust gas containing mercury is brought into contact with activated carbon with chelate adsorption, it is necessary to replenish so that the moisture contained in the activated carbon is not lost, and the exhaust gas does not contain the necessary amount of moisture. In some cases, it is necessary to forcibly replenish.
高温排ガスに水分を補給することにより、吸着剤の水分を、水銀吸着に必要な量以上に維持しながら行なうことは好ましい水銀除去方法である。補給する水分は水または水蒸気によって行なうことができ、水分の補給は例えば超音波噴霧、エアーバブリングによる噴霧、スチームによる補給等の方法を採用できる。 It is a preferable method for removing mercury by supplying moisture to the high-temperature exhaust gas while maintaining the moisture in the adsorbent at an amount higher than that necessary for mercury adsorption. The replenishing water can be performed with water or water vapor, and water replenishment can be performed by methods such as ultrasonic spraying, air bubbling spraying, and steam replenishment.
水銀を含む高温排ガスをキレート剤が吸着された活性炭とを接触させる方法は特に限定されるものではないが、例えばキレート吸着活性炭を充填塔に充填し、該充填塔に水銀を含有する高温排ガスを通過させキレート吸着活性炭と接触させることによって実施できる。本発明の方法により、処理される高温排ガスの温度は例えば150℃以下である。 The method for bringing the high-temperature exhaust gas containing mercury into contact with the activated carbon on which the chelating agent is adsorbed is not particularly limited. For example, the packed tower is filled with chelate-adsorbed activated carbon, and the high-temperature exhaust gas containing mercury is added to the packed tower. It can be carried out by passing it through and contacting with chelating adsorption activated carbon. The temperature of the hot exhaust gas to be treated by the method of the present invention is, for example, 150 ° C. or less.
水の補給時に-CS-SM基を含むキレート剤の水溶液を水性ミストの状態で補給してもよい。このようにすれば水分補給と同時に活性炭へのキレート剤の吸着量を増加させることができ、水銀のキレート化合物の生成量も増加し、水銀除去効率の向上や、吸着剤の処理倍係数の向上が期待できる。 When the water is replenished, an aqueous solution of a chelating agent containing a -CS-SM group may be replenished in an aqueous mist state. In this way, the amount of chelating agent adsorbed on activated carbon can be increased at the same time as hydration, the amount of mercury chelate compound generated also increases, the mercury removal efficiency improves, and the treatment multiplication factor of the adsorbent increases. Can be expected.
活性炭に吸着したキレート剤で水銀ガスがなぜ除去されるかについては定かではないが、活性炭に吸着した水銀が水銀イオンに変化し、活性炭に吸着したキレート剤とキレート化反応を起こすものと思われる。 It is not clear why the chelating agent adsorbed on the activated carbon removes mercury gas, but the mercury adsorbed on the activated carbon changes to mercury ions, which seems to cause a chelation reaction with the chelating agent adsorbed on the activated carbon. .
次に実施例を示すが、本発明はこれらに限定されるものではない。また以下の説明において％は特に断りのない限り重量％である。 Examples are shown below, but the present invention is not limited thereto. In the following description, “%” means “% by weight” unless otherwise specified.
（実施例１〜３）
５％ピペリジンジチオカルバミン酸カリウム水溶液、５％チオモルホリンジチオカルバミン酸カリウム水溶液、及び５% 1,4-ピペラジンジカルボジチエートカリウム水溶液をそれぞれ8メッシュの活性炭300gに流下せしめて、その表面に十分吸着させた。風乾後、その吸着量は12〜14％であり、水分を約５％含有していた。これらのキレート剤を吸着せしめた活性炭を内径2.5cmのガラス製カラムに、高さ20cm充填した。カラムとカラムに接続され水銀含有空気をカラムに供給する配管をヒーターで加熱し、カラム内の測定点温度が100℃、120℃または150℃に調整した。カラムにはHg濃度3mg/m3を含む空気を、水銀含有空気供給配管を通じて供給し、また水分をエアーバブリングにより６g/dayの供給速度で水銀含有空気供給配管を通じてカラムに供給した。カラムに供給する水銀含有空気の流速を７m/minとし、カラム出口空気の水銀濃度を測定した。その結果を表１に示す。１２時間後及び１００時間後の出口水銀濃度は十分に低い値であり、本発明吸着剤が有効に作用していることが分かった。
5% piperidine dithiocarbamate aqueous solution, 5% thiomorpholine potassium dithiocarbamate aqueous solution, and 5% 1,4-piperazine dicarbodithiate aqueous potassium solution were each allowed to flow down into 300 g of 8 mesh activated carbon and fully adsorbed on the surface. . After air drying, the adsorption amount was 12-14% and contained about 5% moisture. Activated carbon adsorbed with these chelating agents was packed in a glass column having an inner diameter of 2.5 cm and a height of 20 cm. A pipe connected to the column and supplying mercury-containing air to the column was heated with a heater, and the measurement point temperature in the column was adjusted to 100 ° C, 120 ° C, or 150 ° C. The column was supplied with air containing an Hg concentration of 3 mg / m 3 through a mercury-containing air supply pipe, and water was supplied to the column through the mercury-containing air supply pipe at a supply rate of 6 g / day by air bubbling. The flow rate of mercury-containing air supplied to the column was 7 m / min, and the mercury concentration in the column outlet air was measured. The results are shown in Table 1. The outlet mercury concentration after 12 hours and after 100 hours was a sufficiently low value, and it was found that the adsorbent of the present invention works effectively.
（実施例４）
実施例３と同様の方法で５％1,4-ピペラジンジカルボジチエートカリウム水溶液を8メッシュの活性炭表面に十分吸着させた。1,4-ピペラジンジカルボジチエートカリウムを吸着せしめた活性炭を内径2.5cmのガラス製カラムに、高さ20cm充填し、110℃でのHg含有空気の水銀吸着特性を調べた。カラム内の測定点温度を110℃に調製し、Hg濃度3mg/m3の水銀含有空気を流速７m/minで供給した。エアーバブリングによるカラムへの水分の供給は６g/dayであった。カラム通過後の空気の水銀濃度は図１のようになり、 出口Hg濃度を 0.05mg/m3以下にすることができる処理倍係数（通過ガス容積と充填物容積の比）は4600×103L/L-吸着剤であった。
Example 4
In the same manner as in Example 3, 5% 1,4-piperazine dicarbodithiate aqueous solution was sufficiently adsorbed on the surface of 8 mesh activated carbon. Activated carbon adsorbed with potassium 1,4-piperazinedicarbodithiate was packed in a glass column with an inner diameter of 2.5 cm and a height of 20 cm, and the mercury adsorption characteristics of Hg-containing air at 110 ° C. were investigated. The measurement point temperature in the column was adjusted to 110 ° C., it was fed mercury-containing air the
（比較例1）
実施例３と同様に５％1,4-ピペラジンジカルボジチエートカリウム水溶液を8メッシュの活性炭に吸着せしめ、内径2.5cmのカラムに高さ20cm充填し、水分の供給を行なわない場合の、110℃でのHg含有空気の水銀吸着特性を調べた。カラム内の測定点温度110℃に設定し、カラムへの水分の供給は行なわずに、Hg濃度3mg/m3の水銀含有空気を流速７m/minで供給したところ、カラム出口空気のHg濃度を0.05mg/m3以下にすることができる処理倍係数は150×103 L/L-吸着剤であり、その後Hg濃度は急激に立ち上がってきた。
(Comparative Example 1)
In the same manner as in Example 3, 5% 1,4-piperazine dicarbodithiate aqueous solution was adsorbed onto 8 mesh activated carbon, packed in a column with a 2.5 cm inner diameter and 20 cm in height, and no water was supplied. The mercury adsorption characteristics of Hg-containing air at ℃ were investigated. When the measurement point temperature in the column was set to 110 ° C and mercury-containing air with an Hg concentration of 3 mg / m 3 was supplied at a flow rate of 7 m / min without supplying water to the column, the Hg concentration of the column outlet air was The processing multiplication factor that can be reduced to 0.05 mg / m 3 or less is 150 × 10 3 L / L-adsorbent, and thereafter the Hg concentration rose rapidly.
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