JPH06126132A - Method for treating exhaust gas with carbon material - Google Patents
Method for treating exhaust gas with carbon materialInfo
- Publication number
- JPH06126132A JPH06126132A JP4301624A JP30162492A JPH06126132A JP H06126132 A JPH06126132 A JP H06126132A JP 4301624 A JP4301624 A JP 4301624A JP 30162492 A JP30162492 A JP 30162492A JP H06126132 A JPH06126132 A JP H06126132A
- Authority
- JP
- Japan
- Prior art keywords
- ammonia
- carbon material
- exhaust gas
- desulfurization
- sox
- 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
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
Landscapes
- Treating Waste Gases (AREA)
- Exhaust Gas Treatment By Means Of Catalyst (AREA)
- Devices And Processes Conducted In The Presence Of Fluids And Solid Particles (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、ＳＯｘ及びＮＯｘを含
有する排ガス、特にＳＯｘの含有量は多いが、その割り
に除去すべきＮＯｘの量が少ない排ガスの処理に適した
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 an exhaust gas treatment method suitable for treating exhaust gas containing SOx and NOx, particularly exhaust gas containing a large amount of SOx but a small amount of NOx to be removed. .
【０００２】[0002]
【従来の技術】各種化石燃料の燃焼排ガスあるいは製鉄
所の焼結炉排ガス等のＳＯｘ及びＮＯｘを含有する排ガ
スの処理方法として、これらの排ガスにアンモニアを添
加し、炭素材の移動層を直交流で通過させて接触させ、
ＳＯｘを吸着させるとともにＮＯｘを分解除去する方法
がある。この方法において、ＳＯｘは主として硫酸の形
で炭素材上に吸着される。そのため、排ガス中に含まれ
るＳＯｘの量が多いと、添加したアンモニアはアンモニ
ウム塩の形で消費されてしまうので脱硝反応に寄与する
アンモニアの量が少なくなり、脱硝反応を進行させるた
めには多量のアンモニアを添加する必要があり、経済的
ではない。また、移動層内の、特に排ガス入口側にアン
モニウム塩が析出し、炭素材をブロック化させ、移動層
内での円滑な移動を阻害する、炭素材の再生時に多量の
アンモニアが発生し、装置の腐食や回収される硫黄等の
副産物を汚染するという問題がある。2. Description of the Related Art As a method for treating exhaust gas containing SOx and NOx, such as exhaust gas from combustion of various fossil fuels or exhaust gas from a sintering furnace of a steel mill, ammonia is added to these exhaust gas and a moving bed of carbon material is cross-flowed. And let it come in contact with
There is a method of adsorbing SOx and decomposing and removing NOx. In this method, SOx is adsorbed on the carbonaceous material mainly in the form of sulfuric acid. Therefore, if the amount of SOx contained in the exhaust gas is large, the added ammonia will be consumed in the form of ammonium salt, and the amount of ammonia that contributes to the denitration reaction will be small. Ammonia needs to be added, which is not economical. In addition, ammonium salts are deposited in the moving bed, especially on the exhaust gas inlet side, and block the carbon material, which hinders smooth movement in the moving bed. However, there is a problem that it corrodes the by-products and the by-products such as recovered sulfur.
【０００３】このような問題を解決する方法として、Ｓ
Ｏｘの含有量の多い、ＳＯｘ及びＮＯｘを含有する排ガ
スを処理する場合に、２個の移動層反応器を設置し、排
ガスにアンモニアを添加するか又は不添加のまま第１の
移動層に供給して主として脱硫を行い、ＳＯｘの量を１
００ｐｐｍ程度以下に減少させ、次いでアンモニアを添
加したのち第２層へ供給して主として脱硝を行うととも
に残りのＳＯｘを除去する方法がある。この方法は、多
量のＳＯｘを含み、しかも除去すべきＮＯｘの含有量の
多い排ガスを処理する場合には極めて有効な方法であ
る。ところが、実際の排ガスの中には、ＳＯｘの含有量
が多い割りにはＮＯｘの含有量が少ない場合が多く、ま
た、排ガスの処理に当たってＮＯｘの全量を除去する必
要はない場合も多い。このような場合には、２個の移動
層反応器を設置するのは非効率的であり、１個の反応器
で処理できる方法が望まれていた。また、これらの方法
においては、いずれも遊離のアンモニアの存在下で脱硝
反応を行わせるため、処理済みの排ガス中にアンモニア
が混入してくるという、いわゆるリークアンモニアの問
題がある。As a method for solving such a problem, S
When treating exhaust gas containing a large amount of Ox and containing SOx and NOx, two moving bed reactors are installed, and ammonia is added to the exhaust gas or supplied to the first moving bed without adding ammonia. And desulfurization is mainly performed, and the amount of SOx is reduced to 1
There is a method of reducing the amount to about 00 ppm or less, then adding ammonia, and then supplying it to the second layer to mainly perform denitration and remove the remaining SOx. This method is an extremely effective method when treating an exhaust gas containing a large amount of SOx and having a large NOx content to be removed. However, in actual exhaust gas, the SOx content is large, but the NOx content is often low, and in many cases, it is not necessary to remove all the NOx in treating the exhaust gas. In such a case, it is inefficient to install two moving bed reactors, and a method capable of treating with one reactor has been desired. Further, in all of these methods, the denitration reaction is carried out in the presence of free ammonia, so that there is a problem of so-called leak ammonia in which ammonia is mixed into the treated exhaust gas.
【０００４】さらに、このような脱硫脱硝方法において
生ずる問題点を解決するため、アンモニアの添加方法を
工夫する試みもなされている。例えば、ＳＯｘ及びＮＯ
ｘを含有する排ガスにアンモニアを添加し炭素質吸着材
の移動層に供給すると、特に温度の低い場合などには、
排ガスの入口近くで多量のアンモニウム塩が生成し、そ
れによって吸着材の粉化が促進されるという問題を解決
する方法として、アンモニアは排ガス中に直接添加する
のではなく、予めアンモニアを吸着させた吸着材を移動
層に供給する方法が提案されている（特開平２−２６６
１８号公報など）。この方法によれば、アンモニアは層
内に均一に供給されるので、部分的にアンモニウム塩が
過剰に生成することはなく吸着材の粉化は少なくなり、
また、ガス後流側のアンモニアはＳＯｘに消費されるこ
となく脱硝に使用されるという利点がある。しかしなが
らこの場合も、ＳＯｘに見合った量のアンモニアがＳＯ
ｘとの反応により消費される、リークアンモニアがある
などの問題は排ガス中に直接アンモニアを入れる場合と
大差はない。Further, in order to solve the problems that occur in such a desulfurization and denitration method, attempts have been made to devise a method for adding ammonia. For example, SOx and NO
When ammonia is added to the exhaust gas containing x and supplied to the moving bed of the carbonaceous adsorbent, especially when the temperature is low,
As a method of solving the problem that a large amount of ammonium salt is generated near the exhaust gas inlet, which promotes the pulverization of the adsorbent, ammonia is not directly added to the exhaust gas, but ammonia is adsorbed in advance. A method of supplying the adsorbent to the moving bed has been proposed (Japanese Patent Laid-Open No. 2-266).
No. 18, etc.). According to this method, ammonia is uniformly supplied in the layer, so that the ammonium salt is not partially excessively produced and the pulverization of the adsorbent is reduced,
Further, there is an advantage that ammonia on the gas downstream side is used for denitration without being consumed by SOx. However, also in this case, the amount of ammonia commensurate with SOx is SO
Problems such as consumption by the reaction with x and the presence of leaked ammonia are not so different from the case where ammonia is directly introduced into the exhaust gas.
【０００５】また、２個の移動層反応器を使用する方法
において、不活化した炭素質触媒を加熱再生したのちア
ンモニア処理して触媒活性を高めるという方法もある
（特開昭６０−２２０１２９号公報など）。しかしなが
らこの方法も、本質的には、前出の２個の移動層反応器
を設置し、排ガスにアンモニアを添加するか又は不添加
のまま第１の移動層に供給して主として脱硫を行い、Ｓ
Ｏｘの量を１００ｐｐｍ程度以下に減少させ、次いでア
ンモニアを添加したのち第２層へ供給して主として脱硝
を行うとともに残りのＳＯｘを除去する方法と変わりは
ない。Further, in a method using two moving bed reactors, there is also a method in which an inactivated carbonaceous catalyst is heated and regenerated, and then treated with ammonia to enhance the catalytic activity (Japanese Patent Laid-Open No. 60-220129). Such). However, also in this method, essentially, the above-mentioned two moving bed reactors are installed, and ammonia is added to the exhaust gas or is fed to the first moving bed without adding ammonia to mainly perform desulfurization, S
There is no difference from the method in which the amount of Ox is reduced to about 100 ppm or less, and then ammonia is added and then supplied to the second layer to mainly perform denitration and remove the remaining SOx.
【０００６】[0006]
【発明が解決しようとする課題】本発明の目的は、前記
従来技術における、ＳＯｘとの反応によるアンモニアの
浪費、アンモニウム塩の析出による炭素材の移動層の流
れの阻害、処理済み排ガス中へのアンモニアの混入等の
問題がない、１個の移動層反応器を用いた簡明な排ガス
処理方法を提供することにある。DISCLOSURE OF THE INVENTION It is an object of the present invention to waste ammonia by reaction with SOx, obstruct the flow of a carbonaceous material moving bed due to precipitation of ammonium salt, and to dispose into treated exhaust gas in the above-mentioned prior art. An object of the present invention is to provide a simple exhaust gas treatment method using one moving bed reactor, which does not have a problem such as the mixing of ammonia.
【０００７】[0007]
【課題を解決するための手段】本発明は、ＳＯｘ及びＮ
Ｏｘ含有排ガスを炭素材と接触させて脱硫及び脱硝を同
時に行う排ガスの処理方法において、ＳＯｘの含有量が
１００ｐｐｍ以上であるＳＯｘ及びＮＯｘ含有排ガス
を、アンモニアを添加することなく、除去すべきＮＯｘ
をＮＯ2 に換算しその３ｍｇに対し１ｇ以上の炭素材が
流下する炭素材の移動層よりなる脱硫脱硝塔内を直交流
で通過させて脱硫、脱硝を行い、脱硫脱硝塔を出た炭素
材は、再生反応器中で加熱再生したのち４００〜６００
℃の温度範囲でアンモニアと接触させて処理し、このア
ンモニア処理した炭素材を前記脱硫脱硝塔に供給するこ
とを特徴とする排ガス処理方法である。The present invention relates to SOx and N
In a method of treating an exhaust gas in which an Ox-containing exhaust gas is brought into contact with a carbon material to perform desulfurization and denitration at the same time, SOx and NOx-containing exhaust gas having a SOx content of 100 ppm or more should be removed without adding ammonia.
Is converted into NO 2 and 3 g of the carbon material is desulfurized and denitrated by passing through a desulfurization and denitration tower composed of a moving bed of carbon materials in which 1 g or more of the carbon material flows down in a cross flow, and the carbon material exits the desulfurization and denitration tower Is 400 to 600 after being heated and regenerated in the regeneration reactor.
In the exhaust gas treatment method, the treatment is carried out by contacting with ammonia in a temperature range of ° C, and the ammonia-treated carbon material is supplied to the desulfurization and denitration tower.
【０００８】本発明の方法で処理対象とする排ガスは、
ＳＯｘの含有量が１００ｐｐｍ以上であり、かつ除去す
べきＮＯｘの量が比較的少ない排ガスである。この方法
で処理できる排ガス中のＮＯｘ含有量の許容範囲は、炭
素材の供給量や反応温度などの運転条件及び処理済みの
排ガス中に許容されるＮＯｘの含有率によって定まるも
のであって一概にはいえないが、除去すべきＮＯｘの量
が移動層中の炭素材１ｇに対し３ｍｇ以下であれば、本
発明の方法により十分処理が可能である。The exhaust gas to be treated by the method of the present invention is
The exhaust gas has a SOx content of 100 ppm or more and a relatively small amount of NOx to be removed. The permissible range of NOx content in exhaust gas that can be treated by this method is determined by operating conditions such as the supply amount of carbonaceous material and reaction temperature, and the NOx content percentage allowed in treated exhaust gas. However, if the amount of NOx to be removed is 3 mg or less with respect to 1 g of the carbonaceous material in the moving bed, sufficient treatment can be performed by the method of the present invention.
【０００９】また、本発明で使用する炭素材としては、
移動層反応器内で使用できる強度を有する活性炭素材で
あれば特に制限なく使用できるが、石炭を予備乾留して
得られる半成コークスを主原料とし、これに副原料とし
て粘結性を有する石炭及び結合剤を添加して混合、混練
したのち成形、乾留、賦活して得られる成形活性コーク
スが特に好適である。Further, as the carbon material used in the present invention,
Any activated carbon material having strength that can be used in a moving bed reactor can be used without particular limitation, but semi-coke obtained by preliminary carbonization of coal is used as a main raw material, and coal having a caking property as an auxiliary raw material. Further, a molding activated coke obtained by adding a binder, mixing, kneading, molding, dry distillation and activation is particularly preferable.
【００１０】以下、本発明の方法について、図１の本発
明の排ガス処理方法によるフローの１例を示す概略図に
従い、詳細に説明する。ＳＯｘの含有量が１００ｐｐｍ
以上であるＳＯｘ及びＮＯｘ含有排ガスを、アンモニア
を添加することなく、排ガスライン３から脱硫脱硝塔１
に供給し、塔内を上方から下方へ移動する炭素材の移動
層中を炭素材の流れに対し直交流で通過させる。炭素材
と接触する間に排ガス中のＳＯｘ及びＮＯｘは吸着ある
いは分解除去され、処理済みの排ガスは系外へ排出され
る。Hereinafter, the method of the present invention will be described in detail with reference to the schematic diagram of FIG. 1 showing an example of the flow of the exhaust gas treatment method of the present invention. SOx content is 100ppm
The above SOx and NOx-containing exhaust gas is desulfurized and denitrated from the exhaust gas line 3 without adding ammonia.
And is passed through the moving bed of the carbonaceous material moving in the tower from the upper side to the lower side in a flow orthogonal to the flow of the carbonaceous material. During contact with the carbon material, SOx and NOx in the exhaust gas are adsorbed or decomposed and removed, and the treated exhaust gas is discharged to the outside of the system.
【００１１】脱硫脱硝塔１内を流下し、ＳＯｘを吸着し
て不活性化した炭素材は脱硫脱硝塔の下部から排出さ
れ、不活性化炭素材ライン４を経て再生塔２へ導かれ
る。そして再生塔上部の再生部２ａにて４００〜６００
℃に加熱、再生される。ここで発生したＳＯ2 を高濃度
で含有するガスは、ＳＯ2 含有ガスライン７より排出さ
れ、副生物回収工程へ送られ高純度のＳＯ2 ガス、硫黄
あるいは硫酸等の副生物が回収される。再生温度が４０
０℃未満では再生に長時間を要したり、再生が不十分と
なる恐れがあり、また、６００℃を超えると活性炭素材
料の表面性状が変化し、脱硝率が低下するので好ましく
ない。The carbon material flowing down in the desulfurization denitration tower 1 and adsorbing SOx and inactivated is discharged from the lower part of the desulfurization denitration tower 1 and is guided to the regeneration tower 2 through the deactivated carbon material line 4. And 400-600 in the regeneration section 2a above the regeneration tower
Heated to ℃ and regenerated. The gas containing SO 2 at a high concentration generated here is discharged from the SO 2 containing gas line 7 and sent to the by-product recovery step to recover high-purity SO 2 gas and by-products such as sulfur and sulfuric acid. . Regeneration temperature is 40
If the temperature is lower than 0 ° C, the regeneration may take a long time or the regeneration may be insufficient, and if the temperature exceeds 600 ° C, the surface property of the activated carbon material is changed and the denitration rate is lowered, which is not preferable.
【００１２】加熱再生された炭素材は、再生塔の後流側
のアンモニア処理部２ｂ内でアンモニア供給ライン６か
ら供給されるアンモニアの存在下に、４００〜６００℃
の温度で加熱してアンモニア処理されたのち、冷却部２
ｃを経て再生塔から排出され、活性炭素材ライン５を通
って脱硫脱硝塔へ送られ、循環使用される。循環中に消
耗した活性炭素材は、系外から適宜新しい炭素材を供給
することによって補充すればよい。ここで使用するアン
モニアの量は、脱硫脱硝塔内において除去すべきＮＯｘ
１モルに対し１〜１．５モルが実用的な範囲である。ア
ンモニア使用量が１モル未満あるいは加熱温度が４００
℃未満では、アンモニア処理の効果が十分ではない。ア
ンモニアの使用量が１．５モルを超えても、超えた分の
アンモニアが脱硝率の向上に寄与する効果は小さい。ま
た、アンモニア処理時の加熱温度が６００℃を超える
と、再生処理時と同様に活性炭素材料の表面性状が変化
し、脱硝率が低下するので好ましくない。The carbon material regenerated by heating is heated to 400 to 600 ° C. in the presence of ammonia supplied from the ammonia supply line 6 in the ammonia treatment section 2b on the downstream side of the regeneration tower.
After being heated at the temperature of 1, and treated with ammonia, the cooling unit 2
It is discharged from the regeneration tower via c, is sent to the desulfurization denitration tower through the activated carbon material line 5, and is used for circulation. The activated carbon material consumed during the circulation may be replenished by appropriately supplying a new carbon material from outside the system. The amount of ammonia used here is NOx to be removed in the desulfurization and denitration tower.
A practical range is 1 to 1.5 mol per mol. Ammonia consumption is less than 1 mol or heating temperature is 400
If the temperature is lower than ° C, the effect of ammonia treatment is not sufficient. Even if the amount of ammonia used exceeds 1.5 mol, the effect of the excess ammonia contributing to the improvement of the denitration rate is small. Further, if the heating temperature during the ammonia treatment exceeds 600 ° C., the surface texture of the activated carbon material changes as in the case of the regeneration treatment, and the denitrification rate decreases, which is not preferable.
【００１３】アンモニア処理は、熱効率の点から再生塔
内で行うのが好都合であるが、再生塔の後にアンモニア
処理装置を設け、そこで行うようにしてもよい。また、
活性炭素材料の再生及びアンモニア処理は、移動層形式
の処理装置を用いて、連続的に行うのが好ましいが、バ
ッチ式の処理装置を用いて行うこともできる。The ammonia treatment is conveniently performed in the regeneration tower from the viewpoint of thermal efficiency, but an ammonia treatment device may be provided after the regeneration tower and may be performed there. Also,
The regeneration of the activated carbon material and the ammonia treatment are preferably carried out continuously using a moving bed type processing apparatus, but can also be carried out using a batch type processing apparatus.
【００１４】このようにしてアンモニア処理した炭素材
は、通常ほとんど遊離アンモニアを含まないが、アンモ
ニアの使用量が多い場合など、炭素材中に含まれる遊離
アンモニアの量が比較的多く、不都合な場合には、不活
性ガスでパージするなどの方法により、遊離アンモニア
の量をさらに減少させることもできる。The carbon material treated with ammonia in this manner usually contains almost no free ammonia, but when the amount of ammonia used is large and the amount of free ammonia contained in the carbon material is relatively large, it is inconvenient. In addition, the amount of free ammonia can be further reduced by a method such as purging with an inert gas.
【００１５】このようにして得られたアンモニア処理炭
素材は、表面が脱硝触媒として十分に活性化されてお
り、これを用いて、ＳＯｘの含有量が１００ｐｐｍ以上
であるＳＯｘ及びＮＯｘ含有排ガスを処理した場合、ア
ンモニアを添加することなく十分な脱硫能力と、炭素材
１ｇ当たり３ｍｇ程度のＮＯｘを分解できる脱硝性能を
有している。The surface of the ammonia-treated carbon material thus obtained is sufficiently activated as a denitration catalyst, and this is used to treat exhaust gas containing SOx and NOx having a SOx content of 100 ppm or more. In this case, it has a sufficient desulfurization ability without adding ammonia and a denitration performance capable of decomposing about 3 mg of NOx per 1 g of carbon material.
【００１６】本発明におけるアンモニア処理は、単にア
ンモニアを炭素材上に吸着させるのではなく、脱硝触媒
としての活性を付与するものである。従って、処理剤の
種類はアンモニアに限定されず、尿素等の還元性のある
窒素化合物を使用することもできるが、アンモニアが最
適である。本発明の方法は、ＳＯｘの含有量が１００ｐ
ｐｍ以上と多いが、除去すべきＮＯｘの含有量が比較的
少ないＳＯｘ及びＮＯｘ含有排ガスの処理に適した方法
であるが、ＳＯｘの含有量が１００ｐｐｍ未満のガスに
ついても有効であることはもちろんである。The ammonia treatment in the present invention is to give an activity as a denitration catalyst, not to simply adsorb ammonia on the carbon material. Therefore, the type of treating agent is not limited to ammonia, and a reducing nitrogen compound such as urea can be used, but ammonia is most suitable. The method of the present invention has a SOx content of 100 p
This method is suitable for treating SOx and NOx-containing exhaust gas, which has a large amount of pm or more, but has a relatively small amount of NOx to be removed, but is, of course, also effective for a gas having a SOx content of less than 100 ppm. is there.
【００１７】[0017]
【実施例】以下、実施例により本発明の方法をさらに具
体的に説明する。 （実施例１）脱硫脱硝反応に繰り返し使用し性能の安定
した活性コークスを用いて試験を行った。この活性コー
クスを用いて脱硫脱硝反応を行い、不活性化した活性コ
ークス３００ｍｌを反応管に充填し、Ｎ2 雰囲気下に５
００℃で１時間加熱して再生した。次いでアンモニア１
６８ｍｇをＮ2 で希釈したガスを導入し５００℃で１時
間加熱しアンモニア処理を行った。このアンモニア処理
活性コークスをＮ2 をパージしながら１４０℃まで冷却
し、ＳＯ2 ５００ｐｐｍ、ＮＯ ４０ｐｐｍ、Ｏ2５
％、Ｈ2 Ｏ ７％、残りＮ2 の組成の混合ガスを導入
し、ＳＶ ４００ Hr-1、温度１４０℃の固定床で脱硫
脱硝試験を行った。EXAMPLES The method of the present invention will be described in more detail below with reference to examples. (Example 1) A test was carried out using active coke which was repeatedly used for desulfurization and denitration reaction and had stable performance. A desulfurization and denitration reaction was carried out using this activated coke, and 300 ml of inactivated activated coke was charged into a reaction tube, and the reaction tube was put under an N 2 atmosphere for 5
It was regenerated by heating at 00 ° C for 1 hour. Then ammonia 1
A gas prepared by diluting 68 mg of N 2 was introduced, and the mixture was heated at 500 ° C. for 1 hour for ammonia treatment. The ammonia-treated activated coke was cooled to 140 ° C. while purging with N 2 , and SO 2 500 ppm, NO 40 ppm, O 2 5
%, H 2 O 7%, and the balance N 2 were introduced, and a desulfurization denitration test was conducted in a fixed bed at SV 400 Hr −1 and a temperature of 140 ° C.
【００１８】この試験において、２０時間経過後の積分
脱硝率は９０％（この間に除去されたＮＯｘ量は活性コ
ークス１ｇあたり、ＮＯ2 換算で０．９２ｍｇ）であ
り、また、７０時間経過後の積分脱硝率は７０％（この
間に除去されたＮＯｘ量は活性コークス１ｇあたり、Ｎ
Ｏ2 換算で２．５０ｍｇ）であった。また、活性コーク
スの処理に使用したアンモニアの量と、除去されたＮＯ
ｘの量との比率はモル比で、２０時間経過時で２．７５
であり、７０時間経過時では１．０１であった。In this test, the integrated denitration rate after 20 hours was 90% (the amount of NOx removed during this time was 0.92 mg in terms of NO 2 per 1 g of active coke), and after 70 hours had elapsed. The integrated denitration rate is 70% (the amount of NOx removed during this period is N per 1 g of activated coke).
It was 2.50 mg in terms of O 2 . Also, the amount of ammonia used to treat the activated coke and the amount of NO removed
The ratio with the amount of x is a molar ratio of 2.75 after 20 hours.
It was 1.01 after 70 hours.
【００１９】（実施例２）再生温度及びアンモニア処理
温度を４００℃とした他は実施例１と同様に操作し、脱
硫脱硝試験を行った。この試験において、２０時間経過
後の積分脱硝率は７１％（この間に除去されたＮＯｘ量
は活性コークス１ｇあたり、ＮＯ2 換算で０．７２ｍ
ｇ）であり、また、７０時間経過後の積分脱硝率は５０
％（この間に除去されたＮＯｘ量は活性コークス１ｇあ
たり、ＮＯ2 換算で１．７８ｍｇ）であった。また、活
性コークスの処理に使用したアンモニアの量と、除去さ
れたＮＯｘの量との比率はモル比で、２０時間経過時で
３．４９であり、７０時間経過時では１．４２であっ
た。(Example 2) A desulfurization and denitration test was conducted in the same manner as in Example 1 except that the regeneration temperature and the ammonia treatment temperature were 400 ° C. In this test, the integrated denitration rate after 20 hours was 71% (the amount of NOx removed during this period was 0.72 m in terms of NO 2 per 1 g of activated coke).
g), and the integrated denitration rate after 70 hours is 50
% (The amount of NOx removed during this period was 1.78 mg in terms of NO 2 per 1 g of active coke). The molar ratio of the amount of ammonia used to treat the activated coke to the amount of NOx removed was 3.49 after 20 hours and 1.42 after 70 hours. .
【００２０】（比較例１）再生後のアンモニア処理を行
わず、混合ガス中に１５０ｐｐｍのアンモニアを添加し
た他は実施例１と同様に操作し、脱硫脱硝試験を行っ
た。この試験において、２０時間経過後の積分脱硝率は
８４％（この間に供給したアンモニア量は２５４ｍｇで
あり、除去されたＮＯｘ量は活性コークス１ｇあたり、
ＮＯ2 換算で０．８６ｍｇ）であった。また、７０時間
経過後の積分脱硝率は５４％（この間に供給したアンモ
ニア量は８８９ｍｇであり、除去されたＮＯｘ量は活性
コークス１ｇあたり、ＮＯ2 換算で１．９３ｍｇ）であ
った。また、脱硫脱硝反応時に供給したアンモニアの量
と、除去されたＮＯｘの量の比率はモル比で、２０時間
経過時で４．４６であり、７０時間経過時では６．９４
であった。この結果から、実施例１の場合よりもアンモ
ニアの供給量が多いにもかかわらず脱硝率は低くなって
いることが分かる。Comparative Example 1 A desulfurization and denitration test was conducted in the same manner as in Example 1 except that 150 ppm of ammonia was added to the mixed gas without performing ammonia treatment after regeneration. In this test, the integrated denitration rate after 20 hours was 84% (the amount of ammonia supplied during this period was 254 mg, and the amount of NOx removed was 1 g of activated coke,
It was 0.86 mg in terms of NO 2 . The integrated denitration rate after 70 hours was 54% (the amount of ammonia supplied during this period was 889 mg, and the amount of NOx removed was 1.93 mg in terms of NO 2 per 1 g of activated coke). The molar ratio of the amount of ammonia supplied during the desulfurization and denitration reaction to the amount of NOx removed was 4.46 after 20 hours and 6.94 after 70 hours.
Met. From this result, it can be seen that the denitration rate is lower than that in the case of Example 1, even though the supply amount of ammonia is larger.
【００２１】（比較例２）再生後のアンモニア処理を行
わず、混合ガス中に１５０ｐｐｍのアンモニアを添加し
た他は実施例２と同様に操作し、脱硫脱硝試験を行っ
た。この試験において、２０時間経過後の積分脱硝率は
５５％（この間に供給したアンモニア量は２５４ｍｇで
あり、除去されたＮＯｘ量は活性コークス１ｇあたり、
ＮＯ2 換算で０．５６ｍｇ）であった。また、７０時間
経過後の積分脱硝率は２５％（この間に供給したアンモ
ニア量は８８９ｍｇであり、除去されたＮＯｘ量は活性
コークス１ｇあたり、ＮＯ2 換算で０．８９ｍｇ）であ
った。また、脱硫脱硝反応時に供給したアンモニアの量
と、除去されたＮＯｘの量の比率はモル比で、２０時間
経過時で６．８２であり、７０時間経過時では１４．９
９であった。この結果から、実施例２の場合よりもアン
モニアの供給量が多いにもかかわらず脱硝率は低くなっ
ていることが分かる。この試験における、２０時間及び
７０時間経過時点における積分脱硝率及びこの間に除去
されたＮＯｘの量、及び活性コークスの処理に使用した
アンモニアの量と、除去されたＮＯｘの量の比率を表１
に示す。Comparative Example 2 A desulfurization and denitration test was conducted in the same manner as in Example 2 except that 150 ppm of ammonia was added to the mixed gas without performing ammonia treatment after regeneration. In this test, the integrated denitration rate after 20 hours was 55% (the amount of ammonia supplied during this period was 254 mg, and the amount of NOx removed was 1 g of activated coke,
It was 0.56 mg in terms of NO 2 . The integrated denitration rate after 70 hours was 25% (the amount of ammonia supplied during this period was 889 mg, and the amount of NOx removed was 0.89 mg in terms of NO 2 per 1 g of activated coke). The molar ratio of the amount of ammonia supplied during the desulfurization and denitration reaction to the amount of NOx removed was 6.82 after 20 hours and 14.9 after 70 hours.
It was 9. From this result, it can be seen that the denitration rate is lower than that in the case of Example 2, even though the supply amount of ammonia is larger. In this test, the integrated NOx removal rates at 20 hours and 70 hours, the amount of NOx removed during this period, and the ratio of the amount of ammonia used to treat active coke to the amount of NOx removed are shown in Table 1.
Shown in.
【００２２】[0022]
【表１】 [Table 1]
【００２３】[0023]
【発明の効果】本発明の方法によれば、ＳＯｘの含有量
が１００ｐｐｍ以上と多いが、除去すべきＮＯｘの含有
量が比較的少ないＳＯｘ及びＮＯｘ含有排ガスを、脱硫
脱硝反応器内にアンモニアを共存させることなく、１個
の反応器により効率よく脱硫脱硝処理することができ
る。 また、アンモニアがＳＯｘによって消費されるこ
とは全くないので、従来の方法に比較してアンモニアの
使用量は大幅に減少でき、さらに、脱硫脱硝反応器内に
入る遊離アンモニアの量が極めて少ないので、アンモニ
ウム塩の析出等により炭素材がブロック化する恐れもな
く、リークアンモニアの問題も生じないという利点もあ
る。According to the method of the present invention, SOx and NOx-containing exhaust gas having a relatively high SOx content of 100 ppm or more but a relatively small amount of NOx to be removed, and ammonia in the desulfurization and denitration reactor. Desulfurization and denitration treatment can be efficiently carried out by one reactor without coexistence. Further, since ammonia is not consumed by SOx at all, the amount of ammonia used can be greatly reduced compared to the conventional method, and furthermore, the amount of free ammonia entering the desulfurization and denitration reactor is extremely small, There is also an advantage that the carbon material is not blocked by precipitation of ammonium salt and the problem of leaked ammonia does not occur.
【図１】 本発明の排ガス処理方法によるフローの１例
を示す概略図である。FIG. 1 is a schematic diagram showing an example of a flow according to an exhaust gas treatment method of the present invention.
１ 脱硫脱硝塔 ２ 再生塔 ２ａ 再生部 ２ｂ アンモニア処理部 ２ｃ 冷却部 ３ 排ガスライン ４ 不活性化炭素材ライン ５ 活性炭素材ライン ６ アンモニア供給ライン ７ ＳＯ2 含有ガスライン1 desulfurization denitration tower 2 regeneration tower 2a regeneration section 2b ammonia treatment section 2c cooling section 3 exhaust gas line 4 deactivated carbon material line 5 activated carbon material line 6 ammonia supply line 7 SO 2 containing gas line
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.5 識別記号 庁内整理番号 ＦＩ 技術表示箇所 Ｂ０１Ｊ 8/12 ＺＡＢ 9041−4Ｇ ３３１ 9041−4Ｇ (72)発明者 高田 光博 東京都中央区日本橋室町２丁目１番１号 三井鉱山株式会社内─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. 5 Identification code Internal reference number FI Technical indication location B01J 8/12 ZAB 9041-4G 331 9041-4G (72) Inventor Mitsuhiro Takada Nihonbashi Muromachi, Chuo-ku, Tokyo 2-1, 1-1 Mitsui Mining Co., Ltd.
Claims (1)
接触させて脱硫及び脱硝を同時に行う排ガスの処理方法
において、ＳＯｘの含有量が１００ｐｐｍ以上であるＳ
Ｏｘ及びＮＯｘ含有排ガスを、アンモニアを添加するこ
となく、除去すべきＮＯｘをＮＯ2 に換算しその３ｍｇ
に対し１ｇ以上の炭素材が流下する炭素材の移動層より
なる脱硫脱硝塔内を直交流で通過させて脱硫、脱硝を行
い、脱硫脱硝塔を出た炭素材は、再生反応器中で加熱再
生したのち４００〜６００℃の温度範囲でアンモニアと
接触させて処理し、このアンモニア処理した炭素材を前
記脱硫脱硝塔に供給することを特徴とする排ガス処理方
法。1. A method for treating exhaust gas in which SOx and NOx-containing exhaust gas is brought into contact with a carbon material to simultaneously perform desulfurization and denitration, and SOx content is 100 ppm or more.
NOx to be removed from the exhaust gas containing Ox and NOx is converted to NO 2 without adding ammonia, and the amount is 3 mg.
On the other hand, 1 g or more of carbon material flows through a desulfurization denitration tower consisting of a moving bed of carbon material in a cross-flow to perform desulfurization and denitration, and the carbon material exiting the desulfurization denitration tower is heated in a regeneration reactor. A method for treating exhaust gas, which comprises regenerating and then treating by contacting with ammonia in a temperature range of 400 to 600 ° C. and supplying the ammonia-treated carbon material to the desulfurization and denitration tower.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP30162492A JP3360854B2 (en) | 1992-10-15 | 1992-10-15 | Exhaust gas treatment method using carbon material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP30162492A JP3360854B2 (en) | 1992-10-15 | 1992-10-15 | Exhaust gas treatment method using carbon material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH06126132A true JPH06126132A (en) | 1994-05-10 |
| JP3360854B2 JP3360854B2 (en) | 2003-01-07 |
Family
ID=17899189
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP30162492A Expired - Lifetime JP3360854B2 (en) | 1992-10-15 | 1992-10-15 | Exhaust gas treatment method using carbon material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3360854B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4861683A (en) * | 1987-03-25 | 1989-08-29 | Sekisui Kagaku Kogyo Kabushiki Kaisha | Quaternary-containing resin used for magnetic recording media |
-
1992
- 1992-10-15 JP JP30162492A patent/JP3360854B2/en not_active Expired - Lifetime
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4861683A (en) * | 1987-03-25 | 1989-08-29 | Sekisui Kagaku Kogyo Kabushiki Kaisha | Quaternary-containing resin used for magnetic recording media |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3360854B2 (en) | 2003-01-07 |
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