JPH08266859A - Method for desulfurizing and denitrating waste gas using manganese ore - Google Patents
Method for desulfurizing and denitrating waste gas using manganese oreInfo
- Publication number
- JPH08266859A JPH08266859A JP7099427A JP9942795A JPH08266859A JP H08266859 A JPH08266859 A JP H08266859A JP 7099427 A JP7099427 A JP 7099427A JP 9942795 A JP9942795 A JP 9942795A JP H08266859 A JPH08266859 A JP H08266859A
- Authority
- JP
- Japan
- Prior art keywords
- desulfurization
- exhaust gas
- denitration
- ore
- reaction tower
- 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.)
- Withdrawn
Links
Landscapes
- Catalysts (AREA)
- Treating Waste Gases (AREA)
- Exhaust Gas Treatment By Means Of Catalyst (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、例えば製鉄所の焼結機
から排出されるような大量の低温排ガスからそれに含ま
れる硫黄酸化物と窒素酸化物を除去（以下、排ガス脱硫
脱硝という）する方法に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention removes sulfur oxides and nitrogen oxides contained in a large amount of low temperature exhaust gas discharged from, for example, a sintering machine of an iron mill (hereinafter referred to as exhaust gas desulfurization denitration). It is about the method.
【０００２】[0002]
【従来の技術】低温排ガスに対して排ガス脱硫脱硝を行
う方法として、特開平６−２１０１３８号公報に示され
るように、鉄鉱石により排ガス脱硫を行った後の排ガス
にアンモニアを添加し、Ｍｎ鉱石を接触還元脱硝触媒と
して利用して排ガス脱硝を行う方法がある。Ｍｎ鉱石は
低温においても接触還元触媒として高い活性を示すた
め、Ｍｎ鉱石を用いる脱硝方法は低温排ガスの脱硝方法
としては優れた方法である。しかしながら、Ｍｎ鉱石の
脱硝性能を効果的に利用するためには、排ガス脱硝に先
立ち排ガス脱硫を行うことが得策である。その理由は、
硫黄酸化物と窒素酸化物を含む排ガス中にアンモニアを
添加してＭｎ鉱石に接触させると脱硝反応（式化１）
と共に脱硫反応（式化２）が起こり、脱硫反応で生成
した硫安〔（ＮＨ4 ）2 ＳＯ4 〕がＭｎ鉱石表面に付着
して、Ｍｎ鉱石の触媒性能を低下させるからである。Ｍ
ｎ鉱石は表面に硫安が付着しても排ガス脱硫（硫安生成
による固定化除去）性能はあまり低下しないが、排ガス
脱硝性能が大幅に低下する。そこで従来の方法では、前
記公報記載のように、予め鉄鉱石を用いて排ガス中の硫
黄酸化物と鉄鉱石中の酸化鉄から亜硫酸鉄、硫酸鉄を生
成させて排ガス脱硫を行い、この脱硫後の排ガスに対し
てアンモニアを添加し、Ｍｎ鉱石を触媒として排ガス脱
硝を行っていた。2. Description of the Related Art As a method for performing exhaust gas desulfurization and denitration on low temperature exhaust gas, as disclosed in JP-A-6-210138, ammonia is added to exhaust gas after exhaust gas desulfurization with iron ore to produce Mn ore. There is a method of performing exhaust gas denitration by utilizing C as a catalytic reduction denitration catalyst. Since Mn ore exhibits high activity as a catalytic reduction catalyst even at low temperatures, the denitration method using Mn ore is an excellent method for denitration of low temperature exhaust gas. However, in order to effectively utilize the denitration performance of Mn ore, it is a good idea to perform exhaust gas desulfurization prior to exhaust gas denitration. The reason is,
When ammonia is added to exhaust gas containing sulfur oxides and nitrogen oxides and brought into contact with Mn ore, denitration reaction (formula 1)
At the same time, a desulfurization reaction (Formula 2) occurs, and ammonium sulfate [(NH 4 ) 2 SO 4 ] produced by the desulfurization reaction adheres to the surface of the Mn ore and reduces the catalytic performance of the Mn ore. M
Even if ammonium sulfate adheres to the surface of n-ore, the exhaust gas desulfurization (immobilization removal by ammonium sulfate generation) performance does not deteriorate significantly, but the exhaust gas denitration performance significantly decreases. Therefore, in the conventional method, as described in the aforementioned publication, iron ore is used in advance to generate iron sulfite and iron sulfate from the sulfur oxides in the exhaust gas and the iron oxide in the iron ore, and the exhaust gas is desulfurized. Ammonia was added to the exhaust gas, and the exhaust gas was denitrified using Mn ore as a catalyst.
【０００３】[0003]
【化１】 ４ＮＯ＋Ｏ2 ＋４ＮＨ3 →４Ｎ2 ＋６Ｈ2 Ｏ …Embedded image 4NO + O 2 + 4NH 3 → 4N 2 + 6H 2 O ...
【０００４】[0004]
【化２】 ＳＯ2 ＋（１／２）Ｏ2 ＋２ＮＨ3 ＋Ｈ2 Ｏ→（ＮＨ4 ）2 ＳＯ4 …Embedded image SO 2 + (1/2) O 2 + 2NH 3 + H 2 O → (NH 4 ) 2 SO 4 ...
【０００５】[0005]
【発明が解決しようとする課題】従来の方法では、脱硫
材と脱硝材にそれぞれ鉄鉱石とＭｎ鉱石という２種類の
材料を用いるため、脱硫材・脱硝材の貯蔵設備や搬入・
搬出・前後処理等のための搬送ラインが２系統必要にな
った。特に大量の排ガス処理においては、それらの貯蔵
・輸送設備の建設とその運転・保守に多大な費用がかか
っていた。In the conventional method, two kinds of materials, iron ore and Mn ore, are used for the desulfurization material and the denitration material, respectively.
Two transport lines for unloading, pre-processing and post-processing are required. Particularly in the case of processing a large amount of exhaust gas, the construction and operation / maintenance of those storage / transportation facilities have been extremely expensive.
【０００６】本発明は、かかる低温排ガスの脱硫脱硝処
理において脱硫材と脱硝材の兼用を図ることにより、脱
硫材・脱硝材の貯蔵・輸送に伴う多大の費用と負荷を大
幅に減少して経済的な排ガス処理を実現するものであ
る。In the present invention, the desulfurization material and the denitration material are used in the desulfurization and denitration treatment of such low temperature exhaust gas, so that the great cost and load associated with the storage and transportation of the desulfurization material and the denitration material are greatly reduced, and the economy is reduced. It realizes effective exhaust gas treatment.
【０００７】[0007]
【課題を解決するための手段】本発明は、硫黄酸化物と
窒素酸化物を含む排ガスを脱硫反応塔に導入して排ガス
脱硫を行い、続いて脱硝反応塔に導入してＭｎ鉱石をア
ンモニア接触還元脱硝触媒として利用して排ガス脱硝を
行う排ガス脱硫脱硝方法において、排ガス脱硝後に脱硝
反応塔から排出されたＭｎ鉱石を脱硫材として脱硫反応
塔に供給するとともに、アンモニアを添加した排ガスを
脱硫反応塔に導入して排ガス脱硫を行うことを特徴とす
るＭｎ鉱石を用いる排ガス脱硫脱硝方法である。その
際、排ガス脱硫後に脱硫反応塔から排出されるＭｎ鉱石
を水洗により再生処理した後、脱硝反応塔に供給して循
環使用することが好ましい。According to the present invention, an exhaust gas containing sulfur oxides and nitrogen oxides is introduced into a desulfurization reaction tower to carry out exhaust gas desulfurization, and subsequently introduced into a denitration reaction tower to contact Mn ore with ammonia. In an exhaust gas desulfurization denitration method for performing exhaust gas denitration using a reduction denitration catalyst, Mn ore discharged from the denitration reaction tower after exhaust gas denitration is supplied to the desulfurization reaction tower as a desulfurization material, and the exhaust gas to which ammonia is added is desulfurization reaction tower It is an exhaust gas desulfurization denitration method using Mn ore, which is characterized in that the exhaust gas desulfurization is carried out by introducing into Mn ore. At this time, it is preferable that Mn ore discharged from the desulfurization reaction tower after exhaust gas desulfurization is regenerated by washing with water and then supplied to the denitration reaction tower for cyclic use.
【０００８】[0008]
【作用】硫黄酸化物と窒素酸化物を含む排ガスには脱硫
反応塔で脱硫された後も通常少量の硫黄酸化物が含まれ
るため、脱硝反応塔で排ガス脱硝に供されるＭｎ鉱石の
表面にわずかずつ硫安が付着する。脱硝反応塔から排出
されたＭｎ鉱石は硫安付着により脱硝性能が低下してい
るが、脱硫に関しては比較的高い性能を維持している。
また、硫安は容易に水に溶解する性質を有する。本発明
はこれらの点に着眼してなされたものである。[Operation] Since the exhaust gas containing sulfur oxides and nitrogen oxides usually contains a small amount of sulfur oxides even after desulfurization in the desulfurization reaction tower, the surface of Mn ore to be subjected to exhaust gas denitration in the denitration reaction tower is Ammonium sulfate adheres little by little. The Mn ore discharged from the denitration reaction tower has a low denitration performance due to the adhesion of ammonium sulfate, but maintains a relatively high performance with respect to desulfurization.
Ammonium sulfate has a property of being easily dissolved in water. The present invention has been made with these points in mind.
【０００９】排ガス脱硝後に脱硝反応塔から排出された
Ｍｎ鉱石は脱硝性能に劣るが、脱硫では十分な性能を有
している。そこで、脱硫反応塔において前記式に従っ
て排ガス中の硫黄酸化物を硫安として固定化除去するた
め、脱硫反応塔に導入前の排ガスに対してアンモニアを
添加するとともに、排ガス脱硝に使用後のＭｎ鉱石を脱
硫反応塔に供給し、これを脱硫材として使用することに
より十分な排ガス脱硫を行うことが可能である。こうし
て、従来脱硝材としてのみ使用されていたＭｎ鉱石が脱
硫材をかねることが可能となり、Ｍｎ鉱石以外の脱硫材
の使用を無くすことができる。Mn ore discharged from the denitration reaction tower after denitration of exhaust gas is inferior in denitration performance, but has sufficient performance in desulfurization. Therefore, in order to immobilize and remove the sulfur oxides in the exhaust gas as ammonium sulfate in the desulfurization reaction tower according to the above formula, ammonia is added to the exhaust gas before being introduced into the desulfurization reaction tower, and the Mn ore used after exhaust gas denitration is removed. It is possible to perform sufficient exhaust gas desulfurization by supplying it to the desulfurization reaction tower and using it as a desulfurization material. In this way, Mn ore, which has been conventionally used only as a denitration material, can also serve as a desulfurization material, and the use of desulfurization materials other than Mn ore can be eliminated.
【００１０】また、脱硫反応塔から排出したＭｎ鉱石
は、表面に付着した硫安を水洗し、乾燥して再生処理し
た後に排ガス処理に循環使用することが可能である。そ
の場合も再生処理したＭｎ鉱石をまず脱硝反応塔で使用
し、続いて脱硫反応塔で使用することにより、Ｍｎ鉱石
以外の脱硫材が不要となる。Further, the Mn ore discharged from the desulfurization reaction tower can be recycled and used for exhaust gas treatment after the ammonium sulfate adhering to the surface is washed with water, dried and regenerated. Also in that case, by using the regenerated Mn ore first in the denitration reaction tower and then in the desulfurization reaction tower, desulfurization materials other than the Mn ore are unnecessary.
【００１１】[0011]
【実施例】以下、本発明の実施例を説明する。Embodiments of the present invention will be described below.
【００１２】図１に実施例を示す。従来アンモニアは脱
硫後の排ガスに対して添加したが、本法では脱硫反応塔
に導入前の排ガスに添加する。脱硫反応塔と脱硝反応塔
は共にＭｎ鉱石を充填した移動層である。排ガスは、ア
ンモニアが添加された後脱硫反応塔に導入され、続いて
脱硝反応塔に導入され、最後に出口から流出する。Ｍｎ
鉱石はまず脱硝反応塔の上部から供給され、塔内で排ガ
ス脱硝に使用された後下部から排出され、引き続き脱硫
反応塔の上部から供給され、塔内で排ガス脱硫に使用さ
れた後下部から排出される。排出後のＭｎ鉱石は水洗に
より表面の硫安を除去した後、製鉄原料として焼結、高
炉、転炉等に使用することができる。FIG. 1 shows an embodiment. Conventionally, ammonia was added to the exhaust gas after desulfurization, but in this method, it is added to the exhaust gas before being introduced into the desulfurization reaction tower. Both the desulfurization reaction tower and the denitration reaction tower are moving beds filled with Mn ore. The exhaust gas is introduced into the desulfurization reaction tower after addition of ammonia, then introduced into the denitration reaction tower, and finally flows out from the outlet. Mn
The ore is first supplied from the upper part of the denitration reaction tower, used in the tower for exhaust gas denitration, and then discharged from the lower part, and subsequently supplied from the upper part of the desulfurization reaction tower, used in the tower for exhaust gas desulfurization, and then discharged from the lower part. To be done. The discharged Mn ore can be used as a raw material for iron making in sintering, blast furnace, converter or the like after removing ammonium sulfate on the surface by washing with water.
【００１３】図１に示す装置を使用し、排ガス流量１
０，０００ｍ3 ／ｈで排ガス脱硫脱硝を行った。排ガス
の温度は１２０℃、ＳＯx とＮＯx の含有量は共に１５
０ｐｐｍであった。アンモニアの注入量は排ガス濃度換
算で４５０ｐｐｍとした。脱硫反応塔、脱硝反応塔は共
に有効容積３ｍ3 で、Ｍｎ鉱石の供給・排出量を各々２
００ｋｇ／ｈとした。この結果、最終的な出口の排ガス
のＳＯx 濃度は３ｐｐｍ、ＮＯx 濃度は６０ｐｐｍとな
り、脱硫率で９８％、脱硝率で６０％が達成された。な
お、脱硫反応塔出口での脱硫率は９０％、脱硝率は２０
％であった。Using the apparatus shown in FIG. 1, the exhaust gas flow rate 1
Exhaust gas desulfurization denitration was performed at 30,000 m 3 / h. The temperature of the exhaust gas is 120 ° C, and the SO x and NO x contents are both 15
It was 0 ppm. The injection amount of ammonia was 450 ppm in terms of exhaust gas concentration. Both the desulfurization reaction tower and the denitration reaction tower have an effective volume of 3 m 3 , and supply and discharge amount of Mn ore is 2 each.
It was set to 00 kg / h. As a result, SO x concentration in the exhaust gas of the final outlet 3 ppm, NO x concentration 60ppm, and the 98% desulfurization rate, 60% in NOx removal efficiency was achieved. The desulfurization rate at the desulfurization reaction tower outlet was 90%, and the denitrification rate was 20%.
%Met.
【００１４】図２にＭｎ鉱石を循環使用する場合のフロ
ーを示す。脱硫反応塔から排出されたＭｎ鉱石は水洗
後、乾燥して再度脱硝反応塔に供給され、循環使用され
る。FIG. 2 shows a flow when Mn ore is recycled. The Mn ore discharged from the desulfurization reaction tower is washed with water, dried, and then supplied again to the denitration reaction tower for cyclic use.
【００１５】図２に示す装置を用いて前記例と同一条件
で排ガス脱硫脱硝を行った結果、最終的な出口の排ガス
のＳＯx 濃度は１５ｐｐｍ、ＮＯx 濃度は７５ｐｐｍと
なり、脱硫率で９０％、脱硝率で５０％が達成された。
なお、脱硫反応塔出口での脱硫率は８０％、脱硝率は１
５％であった。[0015] The using the apparatus shown in FIG examples and results of the exhaust gas desulfurization and denitrification in the same conditions, the final SO x concentration of the exhaust gas outlet 15 ppm, NO x concentration 75ppm, and the desulfurization rate of 90% A denitration rate of 50% was achieved.
The desulfurization rate at the outlet of the desulfurization reaction tower was 80%, and the denitration rate was 1
5%.
【００１６】[0016]
【発明の効果】本発明の排ガス脱硫脱硝方法ではＭｎ鉱
石が脱硫材および脱硝材として兼用され、脱硫材・脱硝
材の貯蔵設備や搬入・搬出・前後処理等のための搬送ラ
インを１系統とすることができ、経済的な排ガス脱硫脱
硝が可能となる。In the exhaust gas desulfurization and denitration method of the present invention, Mn ore is also used as a desulfurization material and a denitration material, and a storage facility for the desulfurization material / denitration material and a transfer line for carrying in / out / post-treatment etc. are provided in one system. Therefore, economical exhaust gas desulfurization and denitration becomes possible.
【図１】本発明を実施するための装置の例を模式的に示
す図である。FIG. 1 is a diagram schematically showing an example of an apparatus for carrying out the present invention.
【図２】本発明を実施するための装置の例を模式的に示
す図である。FIG. 2 is a diagram schematically showing an example of an apparatus for carrying out the present invention.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 庁内整理番号 ＦＩ 技術表示箇所 Ｂ０１Ｄ 53/94 Ｂ０１Ｄ 53/36 １０２Ｅ 53/96 Ｂ０１Ｊ 23/34 (72)発明者 泉水 康幸 富津市新富20−１ 新日本製鐵株式会社技 術開発本部内─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. 6 Identification code Internal reference number FI Technical display location B01D 53/94 B01D 53/36 102E 53/96 B01J 23/34 (72) Inventor Yasuyuki Izumi Futtsu City Shintomi 20-1 Technology Development Division, Nippon Steel Corporation
Claims (2)
脱硫反応塔に導入して排ガス脱硫を行い、続いて脱硝反
応塔に導入してＭｎ鉱石をアンモニア接触還元脱硝触媒
として利用して排ガス脱硝を行う排ガス脱硫脱硝方法に
おいて、排ガス脱硝後に脱硝反応塔から排出されたＭｎ
鉱石を脱硫材として脱硫反応塔に供給するとともに、ア
ンモニアを添加した排ガスを脱硫反応塔に導入して排ガ
ス脱硫を行うことを特徴とするＭｎ鉱石を用いる排ガス
脱硫脱硝方法。1. Exhaust gas containing sulfur oxides and nitrogen oxides is introduced into a desulfurization reaction tower for exhaust gas desulfurization, and subsequently introduced into a denitration reaction tower to utilize Mn ore as an ammonia catalytic reduction denitration catalyst. In the exhaust gas desulfurization denitration method for denitration, Mn discharged from the denitration reaction tower after exhaust gas denitration
An exhaust gas desulfurization denitration method using Mn ore, which comprises supplying ore as a desulfurization material to a desulfurization reaction tower and introducing exhaust gas to which ammonia is added into the desulfurization reaction tower to perform exhaust gas desulfurization.
るＭｎ鉱石を水洗により再生処理した後、脱硝反応塔に
供給して循環使用することを特徴とする請求項１記載の
Ｍｎ鉱石を用いる排ガス脱硫脱硝方法。2. The exhaust gas using Mn ore according to claim 1, wherein the Mn ore discharged from the desulfurization reaction tower after the exhaust gas desulfurization is regenerated by washing with water and then supplied to the denitration reaction tower for recycling. Desulfurization and denitration method.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7099427A JPH08266859A (en) | 1995-04-03 | 1995-04-03 | Method for desulfurizing and denitrating waste gas using manganese ore |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7099427A JPH08266859A (en) | 1995-04-03 | 1995-04-03 | Method for desulfurizing and denitrating waste gas using manganese ore |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH08266859A true JPH08266859A (en) | 1996-10-15 |
Family
ID=14247163
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP7099427A Withdrawn JPH08266859A (en) | 1995-04-03 | 1995-04-03 | Method for desulfurizing and denitrating waste gas using manganese ore |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH08266859A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2002009852A3 (en) * | 2000-08-01 | 2003-02-06 | Enviroscrub Technologies Corp | System and process for removal of pollutants from a gas stream |
| CN105327612A (en) * | 2015-09-25 | 2016-02-17 | 四川大学 | Flue gas low-temperature combined desulfurization and denitration technology method |
| CN109715269A (en) * | 2016-10-14 | 2019-05-03 | 黄华丽 | A kind of purifying agent for harmful gases and its preparation and purification method |
| JP2022525609A (en) * | 2019-03-13 | 2022-05-18 | ネムセドゥク カンパニー リミテッド | Ship exhaust gas purification device and method |
-
1995
- 1995-04-03 JP JP7099427A patent/JPH08266859A/en not_active Withdrawn
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2002009852A3 (en) * | 2000-08-01 | 2003-02-06 | Enviroscrub Technologies Corp | System and process for removal of pollutants from a gas stream |
| CN105327612A (en) * | 2015-09-25 | 2016-02-17 | 四川大学 | Flue gas low-temperature combined desulfurization and denitration technology method |
| CN109715269A (en) * | 2016-10-14 | 2019-05-03 | 黄华丽 | A kind of purifying agent for harmful gases and its preparation and purification method |
| CN109715269B (en) * | 2016-10-14 | 2022-03-08 | 黄华丽 | Harmful gas purifying agent for adsorbing and removing nitrogen oxides in gas flow within temperature range of 60-500 DEG C |
| JP2022525609A (en) * | 2019-03-13 | 2022-05-18 | ネムセドゥク カンパニー リミテッド | Ship exhaust gas purification device and method |
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