JP2003286020A - Highly activated active coke powder and manufacturing method thereof - Google Patents
Highly activated active coke powder and manufacturing method thereofInfo
- Publication number
- JP2003286020A JP2003286020A JP2002088618A JP2002088618A JP2003286020A JP 2003286020 A JP2003286020 A JP 2003286020A JP 2002088618 A JP2002088618 A JP 2002088618A JP 2002088618 A JP2002088618 A JP 2002088618A JP 2003286020 A JP2003286020 A JP 2003286020A
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- Prior art keywords
- activated coke
- exhaust gas
- powder
- coke powder
- highly activated
- Prior art date
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- Treating Waste Gases (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、高賦活活性コーク
ス粉とその製造方法に関し、特に廃棄物焼却炉等から排
出されるダイオキシン類の吸着用噴霧剤として有効な高
賦活活性コークス粉とその製造方法に関するものであ
る。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a highly activated coke powder and a method for producing the same, and more particularly, a highly activated coke powder which is effective as a propellant for adsorbing dioxins discharged from a waste incinerator and the like and its production. It is about the method.
【０００２】[0002]
【従来の技術】硫黄分含有の微粉炭や、石炭系又は石油
系の重質油等を燃料源として使用するボイラーその他の
加熱用燃焼炉等から排出される燃焼排ガス中には、硫黄
酸化物や窒素酸化物等の大気汚染物質が含有されてい
る。かかる硫黄酸化物等を含有する燃焼排ガスの脱硫・
脱硝法としては、燃焼排ガスを水酸化アルカリ水溶液や
アンモニア水溶液等のアルカリ系湿式吸収液で接触洗浄
させて硫黄酸化物等を吸収除去する湿式排煙脱硫法、又
は活性コークスと接触させて硫黄酸化物等を吸着処理す
る乾式排煙脱硫法等が採用されている。2. Description of the Related Art Sulfur oxides are contained in flue gas discharged from pulverized coal containing sulfur, boilers and other heating combustion furnaces that use coal-based or petroleum-based heavy oil as a fuel source. Air pollutants such as nitrogen oxides are contained. Desulfurization of combustion exhaust gas containing such sulfur oxides
As the denitration method, a combustion exhaust gas is subjected to contact cleaning with an alkaline wet absorption solution such as an aqueous alkali hydroxide solution or an aqueous ammonia solution to absorb and remove sulfur oxides, or a flue gas desulfurization method is contacted with activated coke to perform sulfur oxidation. The dry flue gas desulfurization method, which absorbs substances, is used.
【０００３】この内活性コークスによる乾式排煙脱硫法
では、燃焼排ガスを活性コークス粒状物が充填された移
動層式吸着塔に導入して排ガス中に含まれる硫黄酸化物
等の有害物質を活性コークス粒状物に吸着除去させ、吸
着除去後の排気ガスは直接又は集塵装置を経て煙突へ放
出される。一方有害物質を吸着した活性コークス粒状物
は加熱再生処理して循環使用されとともに、加熱再生処
理で分離された硫黄酸化物等は回収装置で酸化されて濃
硫酸や還元して硫黄等の形態で副産物として回収され
る。また再生処理で発生した摩耗粉状物は焼却処理する
か、フライアッシュと共にセメント原料として処理され
ている。In the dry flue gas desulfurization method using active coke, combustion exhaust gas is introduced into a moving bed type adsorption tower filled with activated coke granules, and harmful substances such as sulfur oxides contained in the exhaust gas are activated coke. The particulate matter is adsorbed and removed, and the exhaust gas after the adsorption and removal is discharged to the chimney directly or through a dust collector. On the other hand, the activated coke granules that have adsorbed harmful substances are heated and recycled for reuse, and the sulfur oxides separated by the heating and regeneration treatment are oxidized in a recovery device and concentrated sulfuric acid or reduced to form sulfur etc. Recovered as a by-product. In addition, the abrasion powder generated by the regeneration treatment is incinerated or treated as a cement raw material together with fly ash.
【０００４】一方、都市ゴミ焼却炉、可燃性廃棄物処理
炉、金属精錬工場等の廃棄物焼却炉等から排出される燃
焼廃棄ガス中には、微量の水銀等の重金属を含むばい塵
及び有機化合物等が存在する。ここで有機化合物の中で
も特にポリ塩化ジベンゾダイオキシン（ＰＣＤＤ）、ポ
リ塩化ジベンゾフラン（ＰＣＤＦ）及びコブラナＰＣＢ
に代表されるダイオキシン類は、人体に有害な物質とし
て注目され、法による規制（ダイオキシン類対策特別措
置法ほか）が整いつつある。これらの法規制による構造
基準に従った燃焼状態の改善にもかかわらず、主として
２００℃から３５０℃の温度範囲で、ダイオキシン類が
再合成（デノボ合成）し、ダイオキシン濃度が増加する
などの不具合が発生することが多数報告されている。On the other hand, in the combustion waste gas discharged from municipal waste incinerators, combustible waste treatment furnaces, waste incinerators such as metal smelting factories, etc., dust and organic matter containing a trace amount of heavy metals such as mercury and organic matter. There are compounds and the like. Among the organic compounds, polychlorinated dibenzodioxin (PCDD), polychlorinated dibenzofuran (PCDF) and cobrana PCB
The dioxin, which is represented by, is drawing attention as a substance harmful to the human body, and regulation by the law (Dioxin Special Measures Act etc.) is being established. Despite the improvement of combustion conditions in accordance with the structural standards by these regulations, dioxins are re-synthesized (denovo synthesis) mainly in the temperature range of 200 ° C to 350 ° C, resulting in problems such as an increase in dioxin concentration. Many have been reported to occur.
【０００５】このようなダイオキシン類を除去する方法
としては、焼却炉から排出される排ガスをバグフイルタ
及び活性コークス吸着塔に順次導入して排ガス中に含ま
れるばいじんや有害物質や臭気物質を除去する乾式法が
多数知られている。この場合、排ガスをバグフイルタに
導くに先立って、排ガス中に活性コークス粉末を噴霧す
ることによって、ダイオキシン類及びダイオキシン類の
前駆体及び塩化水素等が吸着もしくは反応によって除去
される。ここで噴霧する活性コークス（又は活性炭）粉
末は、排ガス気流中に均一に分散浮遊すると同時にダイ
オキシン類や重金属等の有害物質を効率よく吸着する高
賦活化したものが望ましい。かかる市販品の活性コーク
ス粉末は必然的に高価であり、大量に継続して消費する
ほどランニングコストの増大を招くことから、活性コー
クスの使用量は可能な限り少なくて済むように吸着性に
優れ、且つより安価なものが望まれている。As a method for removing such dioxins, a dry method is used in which exhaust gas discharged from an incinerator is sequentially introduced into a bag filter and an active coke adsorption tower to remove dust and harmful substances and odorous substances contained in the exhaust gas. Many laws are known. In this case, prior to introducing the exhaust gas to the bag filter, the active coke powder is sprayed into the exhaust gas to remove the dioxins and the precursors of the dioxins, hydrogen chloride and the like by adsorption or reaction. The activated coke (or activated carbon) powder to be sprayed here is preferably highly activated to uniformly disperse and float in the exhaust gas stream and at the same time efficiently adsorb harmful substances such as dioxins and heavy metals. Such commercially available activated coke powder is inevitably expensive, and the more it is consumed continuously, the more the running cost increases. Therefore, the amount of active coke used is excellent so that the adsorbability is low. And, cheaper ones are desired.
【０００６】そこで特開平９−２９０４６号公報には、
都市ゴミ焼却炉からの排ガスをバグフイルタに導くに先
立って、排ガスの気流中に散布吸着剤を吹込み、排ガス
中の有害物質を吸着しバグフイルタにおいて塵埃及び散
布吸着剤を分離除去し、バグフイルタを出た排ガスを活
性コークス吸着塔に導き、排ガス中に残留する有害物質
を吸着剤で吸着除去する方法が提案されている。又特開
平１１−１６９６６４号公報には、バグフイルタでダス
トを除去した後の排ガスの気流中に炭素質吸着剤を吹込
み、引き続き炭素質吸着剤の移動層反応器に導き有害物
質を炭素質吸着剤で吸着除去する方法も提案されてい
る。これら両提案とも、吸着塔から抜き出される活性コ
ークス（炭素質吸着剤）が再生塔において加熱再生さ
れ、再生した活性コークスは篩装置を経て吸着塔に返送
して循環使用し、一方篩装置において活性コークスから
分離した廃活性コークスの粉体をそのまま同一プロセス
での散布吸着剤又は炭素質吸着剤として使用することを
特徴としている。Therefore, Japanese Patent Laid-Open No. 9-29046 discloses that
Before introducing the exhaust gas from the municipal waste incinerator to the bag filter, blow a spray adsorbent into the air flow of the exhaust gas to adsorb the harmful substances in the exhaust gas and separate and remove the dust and spray adsorbent at the bag filter, and then exit the bag filter. A method has been proposed in which the exhaust gas is guided to an activated coke adsorption tower and the harmful substances remaining in the exhaust gas are adsorbed and removed by an adsorbent. Further, in Japanese Patent Application Laid-Open No. 11-169664, a carbonaceous adsorbent is blown into the exhaust gas stream after removing dust with a bag filter, and then the carbonaceous adsorbent is introduced into a moving bed reactor to adsorb harmful substances. A method of adsorbing and removing with a chemical is also proposed. In both of these proposals, the activated coke (carbonaceous adsorbent) extracted from the adsorption tower is heated and regenerated in the regeneration tower, and the regenerated activated coke is returned to the adsorption tower through the sieving apparatus for recycling and is used in the sieving apparatus. The feature is that the powder of waste activated coke separated from the activated coke is used as it is as a spraying adsorbent or a carbonaceous adsorbent in the same process.
【０００７】[0007]
【発明が解決しようとする課題】しかしながら、上記提
案方法で散布吸着剤又は炭素質吸着剤として使用される
廃活性コークス粉体は、従来、廃棄物として処理されて
いたものを使用する点で市販品より安価で有利ではある
が、粒度調整していないことから排ガス気流中に均一に
分散浮遊し難いことと、同じダイオキシン等の排ガス処
理装置で再利用することから細孔容積の増加が少なく再
度のダイオキシン等の吸着用としての賦活活性度が低い
欠点がある。さらに同一プロセスから分離して使用でき
る廃活性コークス量には限度があり、必要な吹込み量の
１／５〜１／２程度しか賄うことができない。従って、
かかる欠点を解消したより安価で賦活活性度が高い活性
コークス粉の開発が強く望まれている。本発明はかかる
現状に鑑み、排ガス中に含有されるダイオキシン類を効
率よく吸着し無害化することができる安価で賦活活性度
が高い活性コークス粉とその製造方法を提供することを
課題とする。However, the waste activated coke powder used as the spraying adsorbent or the carbonaceous adsorbent in the above-mentioned method is commercially available in that it has been treated as waste. Although it is cheaper and more advantageous than the product, it is difficult to uniformly disperse and suspend in the exhaust gas stream because the particle size is not adjusted, and since it is reused in the same exhaust gas treatment device such as dioxin, the increase in pore volume is small and There is a drawback that the activation activity for adsorbing dioxins and the like is low. Furthermore, there is a limit to the amount of waste activated coke that can be used separately from the same process, and only about 1/5 to 1/2 of the required blowing amount can be covered. Therefore,
There is a strong demand for the development of an activated coke powder which eliminates the above drawbacks and is cheaper and has a high activation activity. In view of the present situation, it is an object of the present invention to provide an inexpensive coke powder having a high activation activity and a method for producing the same, which can efficiently adsorb and detoxify dioxins contained in exhaust gas.
【０００８】[0008]
【課題を解決するための手段】本発明者等は、上記課題
について種々検討した結果、前記した燃焼排ガスの乾式
排煙脱硫プロセスで使用される活性コークス粒状物の加
熱再生時に発生する摩耗粉状物は、特に細孔容積が増加
して賦活活性度が高められた状態にあり、粒度調整する
ことでダイオキシン類含有の排ガス処理プロセスにおけ
るダイオキシン類吸着用噴霧剤等として最適に使用でき
ることを見出し本発明を完成した。Means for Solving the Problems As a result of various studies on the above problems, the inventors of the present invention have found that wear powder particles generated during heating regeneration of activated coke granules used in the dry flue gas desulfurization process of combustion exhaust gas described above. In particular, it is found that the product is in a state in which the pore volume is increased and the activation activity is increased, and by adjusting the particle size, it can be optimally used as a propellant for adsorbing dioxins in an exhaust gas treatment process containing dioxins. Completed the invention.
【０００９】即ち、本発明の請求項１に記載の高賦活活
性コークス粉は、乾式排煙脱硫プロセスにおいて硫黄酸
化物含有の燃焼排ガスと接触して硫黄酸化物の吸着と加
熱脱離処理で賦活を高めた再生活性コークス粒状物から
分離した摩耗粉状物であって、平均粒子径が１０〜１５
μｍで、且つ粒子径０．３〜４μｍの含有率が全体の１
０〜２５％に粒度調整されたものであることを特徴とす
る。かかる本発明の高賦活活性コークス粉は、排煙中の
ガス状で存在する硫黄酸化物の吸着と加熱脱離処理の繰
り返しで細孔容積が増加しており、特に最も活性が高い
再生コークス表面からの摩耗粉状物の利用であることか
ら吸着性能が最も向上しており、さらに粒度調整によっ
て排ガス気流中での均一分散浮遊性にも優れていること
から、硫黄酸化物、ダイオキシン類、水銀等の重金属類
等の大きな分子径物質に対して高い吸着性能を発揮でき
る。That is, the highly activated coke powder according to claim 1 of the present invention is activated by adsorption of sulfur oxides and thermal desorption treatment by contact with combustion exhaust gas containing sulfur oxides in a dry flue gas desulfurization process. Which is an abrasion powder separated from regenerated activated coke granules having an increased average particle size of 10 to 15
.mu.m, and the content rate of particle size 0.3-4 .mu.m is 1
It is characterized in that the particle size is adjusted to 0 to 25%. The highly activated coke powder of the present invention has an increased pore volume due to repeated adsorption and thermal desorption treatment of the sulfur oxides present in the flue gas in a gaseous state, and the regenerated coke surface having the highest activity is particularly high. Adsorption performance is the most improved due to the use of abrasion powders from the above, and since it is also excellent in uniform dispersion and suspension in the exhaust gas flow by adjusting the particle size, sulfur oxides, dioxins, mercury It can exhibit high adsorption performance for large molecular diameter substances such as heavy metals.
【００１０】また、本発明の請求項２に記載の高賦活活
性コークス粉は、廃棄物焼却炉等から排出されて１９０
℃以下に冷却された排ガス中に含有されるダイオキシン
類や水銀等の重質金属類の吸着用噴霧剤に使用される請
求項１記載の高賦活活性コークス粉である。かかる本発
明によると、乾式排煙脱硫プロセスとは異なるダイオキ
シン類含有排ガス処理プロセスでの使用であることか
ら、所望の吹込み量が不足することがなく自由に対処で
きる。また、ダイオキシン類を吸着したコークス粉は上
記の粒度調整によってバグフイルタでの圧力損失が少な
く且つバグフイルタろ過面を通過し易い０．３μｍ以下
の微粉末を含まないことから集塵効果を阻害しないし、
更に活性コークスの高い耐着火性（発火温度４５０℃以
上）を継承していることから捕捉された微粉末でバグフ
イルタへの着火防止効果を発揮する。Further, the highly activated coke powder according to claim 2 of the present invention is discharged from a waste incinerator or the like and 190
The highly activated coke powder according to claim 1, which is used as a propellant for adsorbing heavy metals such as dioxins and mercury contained in exhaust gas cooled to a temperature of not more than 0 ° C. According to the present invention, since it is used in a process for treating an exhaust gas containing dioxins, which is different from the dry flue gas desulfurization process, it is possible to freely deal with a desired injection amount without being insufficient. Further, the coke powder having adsorbed dioxins does not hinder the dust collection effect because it does not contain a fine powder of 0.3 μm or less which has a small pressure loss in the bag filter and easily passes through the filter surface of the bag filter by the above particle size adjustment,
Furthermore, since it has inherited the high ignition resistance of the activated coke (ignition temperature of 450 ° C or higher), the captured fine powder exerts the effect of preventing ignition to the bag filter.
【００１１】本発明の請求項３に記載の高賦活活性コー
クス粉の製造方法は、硫黄酸化物含有の燃焼排ガスを、
活性コークス粒状物が吸着材として充填された吸着塔に
導入して硫黄酸化物等を吸着除去させる乾式排煙脱硫プ
ロセスにおける硫黄酸化物等を吸着させた活性コークス
粒状物を不活性ガス雰囲気下で４００℃〜６００℃に加
熱して再生処理し吸着塔へ循環させる際に発生した活性
コークス粒状物の摩耗粉状物を分級処理により平均粒子
径が１０〜１５μｍで、且つ粒子径０．３〜４μｍの含
有率が全体の１０〜２５％に粒度調整することを特徴と
する。The method for producing a highly activated coke powder according to claim 3 of the present invention comprises:
Introduce the activated coke granules adsorbing the sulfur oxides in the dry flue gas desulfurization process, which is introduced into the adsorption tower filled with the activated coke granules as the adsorbent, under the inert gas atmosphere. Abrasion powder of activated coke granules generated when heated to 400 ° C. to 600 ° C., regenerated and circulated to the adsorption tower has an average particle size of 10 to 15 μm and a particle size of 0.3 to The content of 4 μm is characterized in that the particle size is adjusted to 10 to 25% of the whole.
【００１２】上記の製造方法によれば、従来、乾式排煙
脱硫プロセスで大量に発生（発電出力６０万ＫＷ）の石
炭火力発電所で年間約２０００トン程度）していた摩耗
粉状物は、ボイラーでの燃料補助材として焼却処理され
たり、フライアッシュと共にセメント原料として処理さ
れていたものであることから、分級処理工程と適宜粉砕
処理を付加するだけの作業改善で高賦活活性コークス粉
が安価な副産物として得られる。これによって、高価な
市販品の活性炭粉末の購入使用量が大幅に節減され代替
品として優れた経済効果が発揮される。According to the above-mentioned manufacturing method, the abrasion powder which has been conventionally generated in a large amount in the dry flue gas desulfurization process (about 2000 tons per year at a coal-fired power plant with a power generation output of 600,000 kW) is Since it was incinerated as a fuel auxiliary material in a boiler or as a cement raw material together with fly ash, it is possible to improve the work by simply adding a classifying process and crushing process. It is obtained as a by-product. As a result, the purchased amount of expensive activated carbon powder, which is a commercially available product, is significantly reduced, and an excellent economic effect as a substitute product is exhibited.
【００１３】[0013]
【発明の実施の形態】以下、本発明の実施の形態につい
て詳細に説明する。本発明の高賦活活性コークス粉を製
造するのに使用される硫黄酸化物含有の燃焼排ガスと
は、硫黄分含有の微粉炭や、石炭系又は石油系の重質油
等を燃料源とする大型火力発電所のボイラーや各種工業
用加熱炉などの燃焼炉から排出される燃焼排ガスであっ
て、ダイオキシン類は殆ど含有しないが燃料源に起因し
てガス状の硫黄酸化物や窒素酸化物などが含まれ、通常
は熱回収冷却手段で約１５０℃〜１００℃程度の範囲内
にまで冷却されたものである。特に大量の燃焼排ガスが
発生される大型火力発電所のボイラー用加熱炉からの燃
焼排ガスからは、本発明の高賦活活性コークス粉が大量
に得られる点で好ましい。BEST MODE FOR CARRYING OUT THE INVENTION Embodiments of the present invention will be described in detail below. The sulfur oxide-containing combustion exhaust gas used for producing the highly activated coke powder of the present invention is a sulfur-containing pulverized coal or a large-scale fuel source of coal-based or petroleum-based heavy oil or the like. Combustion flue gas discharged from combustion furnaces such as boilers of thermal power plants and various industrial heating furnaces.It contains almost no dioxins but produces gaseous sulfur oxides and nitrogen oxides due to the fuel source. It is included, and is usually cooled to a range of about 150 ° C. to 100 ° C. by a heat recovery cooling means. In particular, the combustion exhaust gas from the heating furnace for a boiler of a large-scale thermal power plant where a large amount of combustion exhaust gas is generated is preferable in that a large amount of the highly activated coke powder of the present invention can be obtained.
【００１４】また、かかる燃焼排ガス中の硫黄酸化物の
吸着に使用される活性コークス（又は活性炭）粒状物と
は、従来から乾式排煙脱硫法に使用されているものであ
れば特に限定されないが、造粒された球形ペレットや円
筒形ペレット状のものであればよく、特に直径１０ｍｍ
φ×長さ１０ｍｍの円筒状ペレットが望ましい。一般に
かかる活性コークス又は活性炭は、木材、褐炭、泥炭、
ヤシの実の殻等を活性化剤としての薬品（塩化亜鉛、り
ん酸など）で処理し乾留するか、或いは木炭などを水蒸
気で活性化して製造された造粒成形品の市販品が使用さ
れる。The activated coke (or activated carbon) granules used for adsorbing sulfur oxides in the combustion exhaust gas are not particularly limited as long as they have been conventionally used in the dry flue gas desulfurization method. , Granulated spherical pellets or cylindrical pellets, especially 10 mm in diameter
A φ × 10 mm long cylindrical pellet is desirable. Generally such activated coke or activated carbon includes wood, lignite, peat,
Commercially available granulated products made by treating palm shells with chemicals as activators (zinc chloride, phosphoric acid, etc.) and carbonizing, or charcoal activated with steam are used. It
【００１５】ここで、本発明の高賦活活性コークス粉を
特定する摩耗粉状物が分離される燃焼排ガスの乾式排煙
脱硫法の一例を図１に従って説明する。一般に硫黄分含
有の石炭や重油等の燃料を使用する燃焼炉から排出され
る燃焼排ガス１は、図示していないボイラー等で熱回収
されて約３７０〜３８０℃となり、更に空気予熱器など
の熱回収手段で約１５０〜１００℃まで冷却されてから
乾式排煙脱硫プロセスに導入される。即ちかかる燃焼排
ガス１は、活性コークス（又は活性炭）粒状物が吸着材
として充填されている移動層式脱硫塔２の低部周辺から
導入して、降下してくる吸着材移動層と直接接触するこ
とで燃焼排ガス中に含まれる硫黄酸化物等の有害物質が
吸着材で吸着除去される。この際、導入される燃焼排ガ
ス中には必要に応じてアンモニアガス３を注入して有害
物質の吸着除去効果を高めることができる。吸着除去処
理後の燃焼排ガスは上部付近から直接又は集塵装置４で
ダストを捕集した後で煙突５へ放出される。An example of the dry flue gas desulfurization method of combustion exhaust gas from which the abrasion powdery substances that specify the highly activated coke powder of the present invention are separated will be described with reference to FIG. Generally, combustion exhaust gas 1 discharged from a combustion furnace that uses a fuel such as sulfur-containing coal or heavy oil is recovered by a boiler (not shown) to a temperature of about 370 to 380 ° C., and the heat of an air preheater or the like. It is cooled to about 150 to 100 ° C. by the recovery means and then introduced into the dry flue gas desulfurization process. That is, the combustion exhaust gas 1 is introduced from around the lower part of the moving bed type desulfurization tower 2 in which activated coke (or activated carbon) particles are filled as an adsorbent, and directly comes into contact with the adsorbent moving bed which is descending. As a result, harmful substances such as sulfur oxides contained in the combustion exhaust gas are adsorbed and removed by the adsorbent. At this time, if necessary, ammonia gas 3 can be injected into the introduced combustion exhaust gas to enhance the effect of adsorbing and removing harmful substances. The combustion exhaust gas after the adsorption removal process is discharged to the chimney 5 directly from the vicinity of the upper part or after the dust is collected by the dust collector 4.
【００１６】一方脱硫塔２の底部から連続的に排出され
る有害物質を吸着した活性コークス粒状物は、移送ライ
ン６から再生塔７に送られる。再生塔７では熱風炉８か
らの熱風により有害物質を吸着した活性コークスは約４
００〜６００℃（４５０℃）に間接加熱され、且つＮ2
ガス等の不活性ガスをキャリアガスとして直接導入され
て硫黄酸化物などが脱離処理される。脱離された硫黄酸
化物はライン９から回収装置１０へ送られ、ここで酸化
されて濃硫酸副産物１１として、或いは還元剤により硫
黄副産物として回収される。硫黄酸化物などが脱離処理
された再生活性コークスは、再生塔７の低部で冷却され
た後で抜き出されて篩装置１２で再生活性コークス粒状
物１３と１ｍｍ以下の摩耗粉状物１４とに分けられる。
篩装置１２のメッシユの篩網目は特に限定するものでは
ないが、通常１ｍｍ以下の摩耗粉状物を分離することが
望ましい。On the other hand, the activated coke granules adsorbing the harmful substances continuously discharged from the bottom of the desulfurization tower 2 are sent from the transfer line 6 to the regeneration tower 7. In the regeneration tower 7, the activated coke that adsorbed harmful substances by the hot air from the hot air stove 8 is about 4
Indirectly heated to 00-600 ℃ (450 ℃) and N2
An inert gas such as a gas is directly introduced as a carrier gas to desorb sulfur oxides and the like. The desorbed sulfur oxide is sent from the line 9 to the recovery device 10, where it is oxidized and recovered as the concentrated sulfuric acid byproduct 11 or as a sulfur byproduct by the reducing agent. The regenerated activated coke from which sulfur oxides and the like have been desorbed is cooled at the lower part of the regeneration tower 7 and then withdrawn, and the regenerated activated coke granules 13 and the abrasion powder 14 having a size of 1 mm or less are sieved by a sieving device 12. Can be divided into
The mesh mesh of the mesh of the sieving device 12 is not particularly limited, but it is usually desirable to separate the abrasion powder of 1 mm or less.
【００１７】篩装置上に残留する再生活性コークス粒状
物１３は、循環ラインから適宜新しい活性コークス補充
品を混合して脱硫塔２に返送し循環再使用される。一
方、篩装置を通過した１ｍｍ以下の摩耗粉状物１４は、
従来はボイラーでの燃料補助材として焼却処理された
り、フライアッシュと共にセメント原料として処理され
ているのが現状であった。本発明ではかかる篩装置下の
摩耗粉状物を、ライン１４から移送して貯蔵サイロ１５
に適宜貯蔵する。かかる摩耗粉状物は図示していない篩
装置又は風力分級機にて分級処理されて特定範囲に粒度
調整することで本発明の高賦活活性コークス粉を得るこ
とができる。分級処理により粒度調整する際に、特定範
囲から除かれる摩耗粉状物は、適宜粉砕処理して分級処
理により利用するか造粒して再生コークスと共に循環使
用してもよい。The regenerated activated coke granules 13 remaining on the sieving unit are appropriately mixed with a new activated coke replenisher from the circulation line and returned to the desulfurization tower 2 for recycling and reuse. On the other hand, the abrasion powder 14 of 1 mm or less that has passed through the sieve device is
Conventionally, it has been incinerated as a fuel auxiliary material in boilers or as a cement raw material together with fly ash. In the present invention, the abrasion powder under the sieving device is transferred from the line 14 to the storage silo 15.
Store as appropriate. The abrasion powder is subjected to classification treatment by a sieve device or an air classifier (not shown) to adjust the particle size within a specific range, whereby the highly activated coke powder of the present invention can be obtained. When the particle size is adjusted by the classification treatment, the abrasion powder that is removed from the specific range may be appropriately pulverized and used by the classification treatment or may be granulated and recycled together with the recycled coke.
【００１８】特に本発明では、１ｍｍ以下の摩耗粉状物
を分級処理により平均粒子径が１０〜１５μｍで、且つ
粒子径０．３〜４μｍの含有率が全体の１０〜２５％、
好ましくは１５％前後に粒度調整することを特徴とす
る。なお粒度調整しない摩耗粉状物そのままでは、排ガ
ス中に含有されるダイオキシン類の吸着用噴霧剤として
使用しても、大きい粒子が含まれて均一浮遊状態が得ら
れず、ダイオキシン類の吸着除去率が下がるし、また
０．３μｍ以下の超微粉末が含有している場合にはバグ
フイルタを容易に通過することから大気汚染上からも好
ましくない。Particularly in the present invention, the abrasion powder of 1 mm or less is classified to have an average particle diameter of 10 to 15 μm, and the content of the particle diameter of 0.3 to 4 μm is 10 to 25% of the whole.
Preferably, the particle size is adjusted to around 15%. It should be noted that if the abrasion powder without particle size adjustment is used as it is, even if it is used as an adsorbent for the adsorption of dioxins contained in the exhaust gas, large floating particles cannot be obtained and a uniform floating state cannot be obtained. When it contains ultrafine powder of 0.3 μm or less, it easily passes through the bag filter, which is not preferable in terms of air pollution.
【００１９】ここで本発明の高賦活活性コークス粉をダ
イオキシン類の吸着用噴霧剤として使用するには、従来
から知られている廃棄物焼却炉等から排出されるダイオ
キシン類含有の排ガスをバグフイルタ及び活性コークス
吸着塔に順次導入して排ガス中に含まれるばいじんや有
害物質や臭気物質を除去する乾式法が望ましい。この場
合排ガス流のバグフイルタへの導入前のラインで噴霧し
てもよいし、またはバグフイルタ出口ラインで噴霧して
もよい。好ましくはバグフイルタへの導入前のラインで
ダイオキシン類の吸着用噴霧剤として使用することが望
ましい。なお、本発明の高賦活活性コークス粉は、燃焼
排ガス中にガス状で存在する硫黄酸化物の吸着と加熱脱
離処理の繰り返しで細孔容積が増加しており、特に最も
活性が高い再生コークス表面からの摩耗粉状物の利用で
あることから吸着性能が最も向上しており、ダイオキシ
ン類の吸着性能が極めて高いことから、バグフイルタへ
の導入ラインで殆どのダイオキシン類が吸着除去される
ので更に活性コークス吸着塔を通過させることなく、そ
のまま煙突へ放出させてもよい。Here, in order to use the highly activated coke powder of the present invention as a propellant for adsorbing dioxins, exhaust gas containing dioxins discharged from a conventionally known waste incinerator or the like is used as a bag filter. It is desirable to use a dry method in which the soot and dust contained in the exhaust gas and harmful substances and odorous substances are sequentially introduced into the activated coke adsorption tower. In this case, spraying may be carried out in the line before introducing the exhaust gas flow into the bag filter, or spraying may be carried out in the bag filter outlet line. It is preferable to use it as a propellant for adsorbing dioxins, preferably in a line before introduction into a bag filter. Incidentally, the highly activated coke powder of the present invention, the pore volume is increased by repeating the adsorption and thermal desorption treatment of the sulfur oxides present in the combustion exhaust gas in a gaseous state, particularly the most active regenerated coke. The adsorption performance is most improved because it is the use of abrasion powder from the surface, and since the adsorption performance of dioxins is extremely high, most of the dioxins are adsorbed and removed in the introduction line to the bag filter, so further Instead of passing through the activated coke adsorption tower, it may be discharged directly to the chimney.
【００２０】[0020]
【実施例】次に本発明の実施例を説明する。なお、下記
実施例で使用したダイオキシン類と水銀の測定方法は下
記に示す。＊ダイオキシン類の測定方法：JIS K0311
「排ガス中のダイオキシン類及びコプラナーＰＣＢの測
定方法」の規定による。＊水銀の測定方法：JIS K0222
「排ガス中の水銀分析方法」の規定による。EXAMPLES Examples of the present invention will be described below. The methods for measuring dioxins and mercury used in the following examples are shown below. * Measuring method for dioxins: JIS K0311
According to the provisions of "Method for measuring dioxins and coplanar PCBs in exhaust gas". * Mercury measurement method: JIS K0222
According to the regulations of "Method for analyzing mercury in exhaust gas".
【００２１】実施例１
（高賦活活性コークス粉の製造）石炭火力発電所（発電
出力６０万ＫＷ）で微粉炭を燃料とするボイラー燃焼炉
からの排ガスを空気予熱器経由で１４０℃以下に冷却し
てから、活性コークス粒状物（直径１０ｍｍφ×長さ１
０ｍｍの円筒状ペレット）が吸着材として充填された移
動層式の吸着塔に導入して硫黄酸化物等を吸着材で吸着
除去し、集塵装置でダストを除去後に煙突ヘ放出させる
乾式排煙脱硫プロセスにおいて、吸着塔で硫黄酸化物等
を吸着させた活性コークス粒状物をキャリヤガス（Ｎ2
ガス）の同伴下、熱風炉からの加熱ガスで約４５０℃前
後となるように間接加熱して再生処理し、冷却後に振動
篩装置にて分級処理される。ここで１ｍｍ以上の篩上物
は吸着塔へ循環使用するとともに、１ｍｍ未満の篩下摩
耗粉状物等を抜き出した。このときの篩下摩耗粉状物等
の平均粒子径は２０μｍ程度、粒子径０．３〜４μｍの
含有率は全体の１０％以下（重量百分率）であった。こ
れを気流分級機にかけて平均粒子径が１３．８μｍで、
且つ粒子径０．３〜４μｍの含有率が全体の１８．１％
になるように分級処理にて粒度調整して高賦活活性コー
クス粉を得た。Example 1 (Production of highly activated coke powder) Exhaust gas from a boiler combustion furnace that uses pulverized coal as a fuel at a coal-fired power plant (power generation output 600,000 kW) is cooled to 140 ° C. or less via an air preheater. Then, activated coke granules (diameter 10 mmφ x length 1
0mm cylindrical pellets) is introduced into a moving bed type adsorption tower filled with adsorbent to adsorb and remove sulfur oxides etc. with the adsorbent, and dust is removed with a dust collector and then discharged to a stack. In the desulfurization process, the activated coke granules having adsorbed sulfur oxides in the adsorption tower are used as carrier gas (N2
Gas), it is indirectly heated with a heating gas from a hot stove to a temperature of about 450 ° C. for regeneration treatment, and after cooling, is classified by a vibrating screen device. Here, the sieved substance having a size of 1 mm or more was circulated to the adsorption tower, and the powder under the sieve having a size of less than 1 mm was extracted. At this time, the average particle size of the undersize powder and the like was about 20 μm, and the content ratio of the particle size of 0.3 to 4 μm was 10% or less (weight percentage) of the whole. This is subjected to an air stream classifier and the average particle size is 13.8 μm.
Moreover, the content of particles having a particle diameter of 0.3 to 4 μm is 18.1% of the whole
The particle size was adjusted by a classification treatment to obtain a highly activated coke powder.
【００２２】（ダイオキシン類除去性能試験）ゴミ廃棄
物等の乾燥ペレット品（ＲＤＦ）を燃料源とする小型ボ
イラー用廃棄物燃焼炉からの排ガスラインに活性コーク
粉を吹込み、バグフイルタに導き集塵処理した後、その
まま煙突へ放出する排ガス処理装置において、バグフイ
ルタ前の１７０〜１８０℃に調節した排ガス気流中に、
上記で得た本発明の高賦活活性コーク粉を（１）１５０
ｍｇ／Ｎｍ3ＤＲＹ、（２）２２０ｍｇ／Ｎｍ3ＤＲＹ、
（３）３２０ｍｇ／Ｎｍ3ＤＲＹの３種類の吹込み量で
吹込んで、ポリ塩化ジベンゾダイオキシン（ＰＣＤＤ）
に代表されるダイオキシン類を活性コーク粉吹込み前の
排ガス気流中のダイオキシン類と水銀に代表される重金
属類の含有率と活性コーク粉吹込み後のバグフイルタ出
口排ガス気流中の同じ含有率を、それぞれJIS K0311とJ
IS K0222の規定により求め、
これより除去率＝｛（１−出口含有率／入口含有率）×
１００｝とする。その結果を表１に示す。なお、この活
性コーク粉のバグフイルタ通過率（粒径０．３μｍ以
下）は０％であった。(Dioxins removal performance test) Activated coke powder is blown into the exhaust gas line from a waste combustion furnace for small boilers that uses dry pellets (RDF) such as garbage waste as a fuel source, and it is guided to a bag filter to collect dust. In an exhaust gas treatment device that directly discharges to a chimney after processing, in an exhaust gas flow adjusted to 170 to 180 ° C. before a bag filter,
The highly activated coke powder of the present invention obtained above is (1) 150
mg / Nm 3 DRY, (2) 220 mg / Nm 3 DRY,
(3) Polychlorinated dibenzodioxin (PCDD) was blown with three types of 320 mg / Nm 3 DRY.
The dioxin represented by the above, the content of heavy metals represented by dioxin and mercury in the exhaust gas flow before the activated coke powder injection and the same content in the bag filter outlet exhaust gas flow after the activated coke powder injection, JIS K0311 and J respectively
Obtained according to the regulations of IS K0222, and from this, removal rate = {(1-outlet content rate / inlet content rate) x
100}. The results are shown in Table 1. The active coke powder had a bag filter passing rate (particle size of 0.3 μm or less) of 0%.
【００２３】比較例１
実施例１で使用した高賦活活性コークス粉に代えて、分
級処理していない篩下摩耗粉状物を（１）１５０ｍｇ／
Ｎｍ3ＤＲＹ、（２）２００ｍｇ／Ｎｍ3ＤＲＹ、（３）
３２０ｍｇ／Ｎｍ3ＤＲＹの３種類の吹込み量で吹込ん
で、ポリ塩化ジベンゾダイオキシン（ＰＣＤＤ）に代表
されるダイオキシン類と水銀に代表される重金属類の除
去率をそれぞれ測定した。その結果を表１に示す。な
お、この活性コーク粉のバグフイルタ通過率（粒径０．
３μｍ以下）も０％であった。Comparative Example 1 Instead of the highly activated coke powder used in Example 1, (1) 150 mg / under-sieving abrasion powder which was not classified
Nm 3 DRY, (2) 200 mg / Nm 3 DRY, (3)
The removal rates of dioxins represented by polychlorinated dibenzodioxins (PCDD) and heavy metals represented by mercury were measured by blowing in three types of 320 mg / Nm 3 DRY. The results are shown in Table 1. In addition, the bag filter passing rate (particle size of 0.
3 μm or less) was also 0%.
【００２４】参考例１
実施例１で使用した高賦活活性コークス粉に代えて、市
販品であるダイオキシン類吸着用噴霧剤（平均粒子径が
１３．２μｍで、且つ粒子径０．３〜４μｍの含有率が
全体の２２．３％（重量百分率））を（１）１５０ｍｇ
／Ｎｍ3ＤＲＹ、（２）２００ｍｇ／Ｎｍ3ＤＲＹ、
（３）３２０ｍｇ／Ｎｍ3ＤＲＹの３種類の吹込み量で
吹込んで、ポリ塩化ジベンゾダイオキシン（ＰＣＤＤ）
に代表されるダイオキシン類と水銀に代表される重金属
類の除去率をそれぞれ測定した。その結果を表１に示
す。なお、この活性コーク粉のバグフイルタ通過率（粒
径０．３μｍ以下）は０％であった。Reference Example 1 Instead of the highly activated coke powder used in Example 1, a commercially available propellant for adsorbing dioxins (having an average particle size of 13.2 μm and a particle size of 0.3 to 4 μm) was used. Content is 22.3% (weight percentage) of the whole (1) 150 mg
/ Nm 3 DRY, (2) 200 mg / Nm 3 DRY,
(3) Polychlorinated dibenzodioxin (PCDD) was blown with three types of 320 mg / Nm 3 DRY.
The removal rates of dioxins typified by and heavy metals typified by mercury were measured. The results are shown in Table 1. The active coke powder had a bag filter passing rate (particle size of 0.3 μm or less) of 0%.
【００２５】[0025]
【表１】 [Table 1]
【００２６】表１の結果から明らかなように、本発明の
高賦活活性コークス粉は、ダイオキシン類の除去率が９
８〜９９％、重金属（水銀）の除去率が９２〜９７％に
達しており、市販品の除去率と遜色がなく優れているこ
とがわかる。一方分級処理しなかった篩下摩耗粉状物で
は、ダイオキシン類の除去率が８２〜９０％、重金属
（水銀）の除去率が８７〜９４％と不安定で市販品より
も低下している。なおバグフイルタを通過する微粉末
（粒径０．３μｍ以下）は０％であった。ちなみに、高
賦活活性コークス粉の吹込み量は、１５０ｍｇ／Ｎｍ3
で十分でありそれ以上に高めても効果の向上はないこと
がわかる。As is clear from the results shown in Table 1, the highly activated coke powder of the present invention has a removal rate of dioxins of 9%.
8 to 99% and the removal rate of heavy metal (mercury) reached 92 to 97%, which is comparable to the removal rate of commercial products and is excellent. On the other hand, in the under-sieve abrasion powder that has not been classified, the removal rate of dioxins is 82 to 90% and the removal rate of heavy metals (mercury) is 87 to 94%, which is unstable and lower than that of commercial products. The fine powder (particle size: 0.3 μm or less) passing through the bag filter was 0%. By the way, the blowing amount of highly activated coke powder is 150 mg / Nm3.
It can be seen that is sufficient, and the effect is not improved even if it is further increased.
【００２７】[0027]
【発明の効果】以上説明した本発明の高賦活活性コーク
ス粉は、排煙中のガス状硫黄酸化物の吸着と加熱脱離処
理の繰り返しで細孔容積が増加し吸着性能が向上してお
り、さらに粒度調整によって排ガス気流中での均一分散
浮遊性に優れていることから、硫黄酸化物、ダイオキシ
ン類等の大きな分子径物質に対して高い吸着性能を発揮
する。また乾式排煙脱硫プロセスで大量に発生していた
摩耗粉状物に分級処理工程を付加するだけで容易に付加
価値を高めた安価な副産物としての高賦活活性コークス
粉が得られる。これによって、高価な市販品の活性炭粉
末の購入使用量が大幅に節減され代替品使用により優れ
た経済効果が発揮される。EFFECTS OF THE INVENTION The highly activated coke powder of the present invention described above has improved adsorption performance due to increase in pore volume due to repeated adsorption and thermal desorption of gaseous sulfur oxides in flue gas. Furthermore, since it is excellent in uniform dispersion and suspension in the exhaust gas stream by adjusting the particle size, it exhibits high adsorption performance for substances with large molecular diameters such as sulfur oxides and dioxins. In addition, a highly activated coke powder as an inexpensive by-product having an increased added value can be easily obtained only by adding a classification treatment step to the abrasion powder that has been generated in a large amount in the dry flue gas desulfurization process. As a result, the purchase amount of expensive commercial activated carbon powder is significantly reduced, and a superior economic effect is achieved by using a substitute.
【図１】本発明の高賦活活性コークス粉を製造するのに
使用される燃焼排ガスの乾式排煙脱硫法の概略プロセス
フローである。FIG. 1 is a schematic process flow of a dry flue gas desulfurization method of combustion exhaust gas used for producing the highly activated coke powder of the present invention.
１ 燃焼排ガス ２ 移動層式脱硫塔 ３ アンモニアガス ４ 集塵装置（バグフイルタ） ５ 煙突 ６ 活性コークス粒状物の移送ライン ７ 再生塔 ８ 熱風炉 ９ 硫黄酸化物含有のオフガスライン １０ 回収装置 １１ 濃硫酸副産物 １２ 篩装置 １３ 再生活性コークス粒状物 １４ 摩耗粉状物 1 combustion exhaust gas 2 Moving bed desulfurization tower 3 Ammonia gas 4 Dust collector (Bag filter) 5 chimney 6 Activated coke granular material transfer line 7 regeneration tower 8 hot stoves 9 Sulfur oxide-containing off-gas line 10 Recovery device 11 Concentrated sulfuric acid by-product 12 Sieve device 13 Regenerated activated coke granules 14 Wear powder
───────────────────────────────────────────────────── 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） Ｂ０１Ｊ 20/34 Ｂ０１Ｄ 53/34 １３６Ａ (72)発明者 外岡 正夫 東京都中央区銀座六丁目15番１号 電源開 発株式会社内 (72)発明者 西山 浩靖 東京都中央区銀座六丁目15番１号 電源開 発株式会社内 (72)発明者 椎屋 光昭 東京都中央区銀座六丁目15番１号 電源開 発株式会社内 (72)発明者 坪谷 久男 東京都中央区銀座六丁目15番１号 電源開 発株式会社内 (72)発明者 神谷 一憲 東京都中央区銀座六丁目15番１号 電源開 発株式会社内 Ｆターム(参考） 4D002 AA21 AA29 AC04 BA04 BA13 DA43 GA01 GB03 4G066 AA04B BA09 BA20 CA31 CA47 DA02 GA06 GA32 4G146 AA06 AA22 AB01 AC02A AC02B AD32 BA34 BB03 BD06 BD19 ─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. 7 Identification code FI theme code (reference) B01J 20/34 B01D 53/34 136A (72) Inventor Masao Tonooka 6-15-1 Ginza, Chuo-ku, Tokyo Power development company (72) Inventor Koyasu Nishiyama 6-15-1, Ginza, Chuo-ku, Tokyo Power development company (72) Inventor Mitsuaki Shiiya 6-15-1, Ginza, Chuo-ku, Tokyo Power supply opening Incorporated company (72) Inventor Hisao Tsuboya 6-15-1, Ginza, Chuo-ku, Tokyo Power source development Incorporated (72) Inventor Kazunori Kamiya 6-15-1, Ginza, Chuo-ku, Tokyo Power source Shares In-house F-term (reference) 4D002 AA21 AA29 AC04 BA04 BA13 DA43 GA01 GB03 4G066 AA04B BA09 BA20 CA31 CA47 DA02 GA06 GA32 4G146 AA06 AA22 AB01 AC02A AC02B AD32 BA34 BB03 BD06 BD19
Claims (4)
物含有の燃焼排ガスと接触して硫黄酸化物の吸着と加熱
脱離処理で賦活を高めた再生活性コークス粒状物から分
離した摩耗粉状物であって、平均粒子径が１０〜１５μ
ｍで、且つ粒子径０．３〜４μｍの含有率が全体の１０
〜２５％に粒度調整されたものであることを特徴とする
高賦活活性コークス粉。1. A wear powder substance separated from regenerated activated coke granules which have been activated in a dry flue gas desulfurization process by contacting with a combustion exhaust gas containing sulfur oxides to increase activation by adsorption and thermal desorption of sulfur oxides. And the average particle size is 10-15μ
m, and the content of particles having a particle diameter of 0.3 to 4 μm is 10
A highly activated coke powder characterized by having a particle size adjusted to -25%.
以下に冷却された排ガス中に含有されるダイオキシン類
や水銀等の重質金属類の吸着用噴霧剤に使用される請求
項１記載の高賦活活性コークス粉。2. 190 ° C. when discharged from a waste incinerator, etc.
The highly activated coke powder according to claim 1, which is used as a propellant for adsorbing heavy metals such as dioxins and mercury contained in the cooled exhaust gas below.
ークス粒状物が吸着材として充填された吸着塔に導入し
て硫黄酸化物等を吸着除去させる乾式排煙脱硫プロセス
における硫黄酸化物等を吸着させた活性コークス粒状物
を不活性ガス雰囲気下で４００℃〜６００℃に加熱して
再生処理し吸着塔へ循環させる際に発生した活性コーク
ス粒状物の摩耗粉状物を分級処理により平均粒子径が１
０〜１５μｍで、且つ粒子径０．３〜４μｍの含有率が
全体の１０〜２５％に粒度調整することを特徴とする高
賦活活性コークス粉の製造方法。3. Sulfur oxides, etc. in a dry flue gas desulfurization process in which sulfur oxide-containing combustion exhaust gas is introduced into an adsorption tower filled with activated coke granules as an adsorbent to adsorb and remove sulfur oxides, etc. Wear particles of the activated coke granules generated when the adsorbed activated coke granules are heated to 400 ° C to 600 ° C under an inert gas atmosphere and regenerated and circulated to the adsorption tower are classified by an average particle. Diameter is 1
A method for producing a highly activated coke powder, characterized in that the content of particles having a particle size of 0 to 15 μm and a particle diameter of 0.3 to 4 μm is adjusted to 10 to 25% of the whole.
を燃料源とする火力発電所のボイラー用燃焼炉から排出
される燃焼排ガスである請求項３記載の高賦活活性コー
クス粉の製造方法。4. The method for producing highly activated coke powder according to claim 3, wherein the sulfur oxide-containing combustion exhaust gas is a combustion exhaust gas discharged from a combustion furnace for a boiler of a thermal power plant using coal powder as a fuel source. .
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| WO2005030641A1 (en) * | 2003-09-26 | 2005-04-07 | Electric Power Development Co., Ltd. | Highly activated coke powder and process for producing the same |
| JP2006075670A (en) * | 2004-09-07 | 2006-03-23 | Electric Power Dev Co Ltd | Dry desulfurizing plant, method for removing mercury therefrom, and regeneration tower |
| JP2007039296A (en) * | 2005-08-05 | 2007-02-15 | Taiheiyo Cement Corp | Method and system for treating exhaust gas in cement manufacturing plant |
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| CN102348491A (en) * | 2009-03-16 | 2012-02-08 | 电源开发工程技术株式会社 | Regeneration column and dry apparatus for discharge gas treatment |
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| KR101257429B1 (en) | 2011-05-03 | 2013-04-23 | 주식회사 포스코 | Device and method for controlling screening size of exhaust sintering gas activated carbon |
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| CN105413326B (en) * | 2015-12-25 | 2017-09-19 | 中冶北方（大连）工程技术有限公司 | A kind of activated coke flue gas purification system |
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