JP3202411B2 - Nitrous oxide treatment method - Google Patents
Nitrous oxide treatment methodInfo
- Publication number
- JP3202411B2 JP3202411B2 JP12582793A JP12582793A JP3202411B2 JP 3202411 B2 JP3202411 B2 JP 3202411B2 JP 12582793 A JP12582793 A JP 12582793A JP 12582793 A JP12582793 A JP 12582793A JP 3202411 B2 JP3202411 B2 JP 3202411B2
- Authority
- JP
- Japan
- Prior art keywords
- nitrous oxide
- catalyst
- ceramic filter
- combustion
- present
- 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.)
- Expired - Lifetime
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
- Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
- Y02C20/00—Capture or disposal of greenhouse gases
- Y02C20/10—Capture or disposal of greenhouse gases of nitrous oxide (N2O)
Landscapes
- Exhaust Gas Treatment By Means Of Catalyst (AREA)
- Catalysts (AREA)
Description
【０００１】[0001]
【産業上の利用分野】本発明は事業用、産業用のボイ
ラ、特に燃焼温度が低い（７００〜９５０℃）加圧流動
床方式のボイラ等より発生する排ガス中の亜酸化窒素
（Ｎ 2 Ｏ）の処理方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to nitrous oxide in exhaust gas generated from a commercial or industrial boiler, particularly a pressurized fluidized bed boiler having a low combustion temperature (700 to 950 DEG C.).
(N 2 O) .
【０００２】[0002]
【従来の技術】Ｎ2 Ｏは地球環境上問題ある物質として
注目され始めたのが比較的最近であるため、その低減方
法については殆ど技術的な検討がなされていないのが現
状である。2. Description of the Related Art N 2 O has recently begun to attract attention as a substance having a problem on the global environment, and there has been little technical study on its reduction method.
【０００３】[0003]
【発明が解決しようとする課題】Ｎ2 Ｏは炭酸ガスと同
様の温室効果を有し、また、フロン（フルオロカーボ
ン）ガスと同様に成層圏のオゾン層破壊の原因物質とな
るために、近時地球規模の環境問題に関連して注目され
るようになった。このＮ2 Ｏは一般に高温度（１３００
℃以上）での燃焼方式（微粉炭燃焼、ガス燃焼、油燃焼
等）では殆ど生じないが、流動床など低温度（７００〜
９００℃）で燃焼させる方式ではかなりの濃度で発生す
ることが一般に認められつつある。Since N 2 O has a greenhouse effect similar to that of carbon dioxide gas, and also causes a destruction of the ozone layer in the stratosphere similarly to flon (fluorocarbon) gas, N 2 O Attention has been focused on environmental issues of scale. This N 2 O is generally high temperature (1300
℃ or above) (pulverized coal combustion, gas combustion, oil combustion, etc.), but hardly occurs, but low temperature (700 ~
It is generally being recognized that combustion at 900 ° C.) produces significant concentrations.
【０００４】本発明は上記技術水準に鑑み、いったん生
成した排ガス中のＮ2 Ｏを簡単な手段によって効率的に
低減する技術を提供しようとするものである。The present invention has been made in view of the above-mentioned state of the art, and aims to provide a technique for efficiently reducing N 2 O in exhaust gas once generated by simple means.
【０００５】[0005]
【課題を解決するための手段】本発明は５５０℃以上の
燃焼排ガス流路中に、除塵用セラミックスフィルタを設
置し、該フィルタの大粒子骨格層にランタニド元素の酸
化物を含むアルミナを主成分とするセラミックスよりな
る亜酸化窒素分解触媒を小粒子として介在させることを
特徴とする燃焼排ガス中の亜酸化窒素の処理方法であ
る。SUMMARY OF THE INVENTION The present invention is in the 5 50 ° C. or more flue gas passage, the dust removing ceramic filter installed, acid lanthanide the large particle skeleton layer of the filter
Ceramics containing alumina as the main component
That Ru nitrous the oxide decomposition catalyst Ah in how to process the nitrous oxide in the combustion exhaust gas, characterized in that the intervention as small particles <br/>.
【０００６】本発明で使用するＮ2 Ｏ分解用触媒はラン
タニド元素を各ランタニド酸化物重量比で５〜３０ｗｔ
％の範囲でＡｌ2 Ｏ3 に混合してなるものである。ラン
タニド酸化物を混合したＡｌ2 Ｏ3 を主成分としたセラ
ミックスを亜酸化窒素分解用触媒として使用する場合
に、その初期触媒活性を高めるためには触媒の比表面積
の増加及び単位面積当たりの活性を高める必要がある
が、ランタニド酸化物添加量が３０ｗｔ％を越えると比
表面積低下が起こることから添加重量比は５〜３０ｗｔ
％の範囲が最適である。The catalyst for decomposing N 2 O used in the present invention contains lanthanide element in an amount of 5 to 30 wt.% By weight of each lanthanide oxide.
% In a range of Al 2 O 3 . When using ceramics in which the Al 2 O 3 were mixed lanthanide oxide as the main component as a nitrous oxide decomposition catalyst, the activity per increase and unit area of the specific surface area of the catalyst to increase its initial catalytic activity However, if the amount of the lanthanide oxide exceeds 30 wt%, the specific surface area decreases.
The range of% is optimal.
【０００７】本発明の排ガス中のＮ2 Ｏの処理方法とし
ては、Ｎ 2 Ｏ分解触媒と防塵用セラミックスフィルタと
を組み合せて行なうことが好ましい。防塵用セラミック
スフィルタの材料としてはアルミナ、マグネシア等の耐
高温性のものが用いられる。 The method for treating N 2 O in exhaust gas of the present invention is preferably carried out by combining an N 2 O decomposition catalyst with a dust-proof ceramic filter. As a material of the dustproof ceramic filter, a high temperature resistant material such as alumina and magnesia is used .
【０００８】[0008]
【作用】Ｎ 2 Ｏは５５０℃以上で、ランタニド元素の酸
化物を含むアルミナを主成分としたセラミックスの作用
により、実用的な速度及び耐久性を維持してＮ 2 とＯ 2
に分解することが本発明者らの実験によって判明した。
以下に、Ｎ 2 Ｏ分解触媒に関する本発明者らの実験結果
について述べる。 [Action] N 2 O is 550 ° C or higher, and acid of lanthanide element
Of ceramics containing alumina as the main component
By maintaining practical speed and durability, N 2 and O 2
It was found by the experiments of the present inventors that the decomposition was carried out.
The following is the experimental results of the present inventors regarding the N 2 O decomposition catalyst.
Is described.
【０００９】Ｎ 2 Ｏ：５３ｐｐｍ、Ｏ2 ３％、残部：Ｎ
2 よりなる供試ガスを標準ガスボンベと浮遊式流量計に
て調整し、磁製反応管（アルミナ製内径２０ｍｍ、有効
加熱長１５０ｍｍ）と電気炉よりなる流動式反応装置を
用いてＮ2 Ｏの分解挙動を調査した。反応時間は０．４
秒、ガス流量は２Ｎリットル／分、またＮ2 Ｏ濃度の分
析はＥＣＤ検出器ガスクロマトグラフによった。表１中
に示す各触媒は球径４ｍｍのものを２０ｇを充填した
が、これは触媒の耐熱性を評価するため予め１，０００
℃で７，０００時間強制熱処理したものである。なお、
比較のため、無充填の試験も併せ実施した。 N 2 O: 53 ppm, O 2 3%, balance: N
The test gas consisting of 2 was adjusted with a standard gas cylinder and a floating flow meter, and N 2 O was measured using a fluidized reactor consisting of a porcelain reaction tube (alumina inner diameter 20 mm, effective heating length 150 mm) and an electric furnace. The decomposition behavior was investigated. Reaction time is 0.4
Seconds, gas flow rate was 2N l / min, and N 2 O concentration was analyzed by ECD detector gas chromatograph. Each of the catalysts shown in Table 1 was filled with 20 g of a catalyst having a spherical diameter of 4 mm.
C. for 7,000 hours. In addition,
For comparison, an unfilled test was also performed.
【００１０】結果を表１に示す。表１に示したように、
Ｎ2 Ｏはこれらの触媒の存在下では５５０℃以上で充分
な耐久性を保持して有効に低減されることが判明した。
なお、出口ガス中のＮＯ、Ｎ2 Ｏ濃度は、いずれの条件
でも１ｐｐｍ以下であり、Ｎ 2 Ｏは無害なＮ2 とＯ2 に
分解されている。The results are shown in Table 1. As shown in Table 1,
NTwoO is sufficient at 550 ° C or higher in the presence of these catalysts
It has been found that the durability is effectively reduced while maintaining excellent durability.
Note that NO, N in the outlet gasTwoO concentration depends on the conditions
However, it is 1 ppm or less and N TwoO is harmless NTwoAnd OTwoTo
Has been disassembled.
【００１１】[0011]
【表１】 触媒Ａ．Ｂ．Ｃはアルミナを主成分とし、それぞれＬａ
2 Ｏ3 ，Ｐｒ2 Ｏ3 ，ＣｅＯ2 を１０ｗｔ％含むもので
ある。[Table 1] Catalyst A. B. C is mainly composed of alumina, each of which is La
It contains 10 wt% of 2 O 3 , Pr 2 O 3 and CeO 2 .
【００１２】[0012]
【実施例】以下、本発明の実施例をあげて本発明をより
詳細に説明する。 （実施例）本発明の一実施例を図１によって説明する。
図１において、１は燃焼炉本体、２は同燃焼炉本体１内
に設けられた流動床燃焼部、３は燃焼用空気の供給ライ
ン、４は流動床燃焼部２へ供給される主燃料である石炭
の供給ライン、５は燃焼炉本体１の上部に接続された未
燃炭素回収用の除塵用セラミックスフィルタとＮ2Ｏ分
解触媒層であり、この５の部分が本発明の主要構成要素
である。一般に除塵用セラミックスフィルタ及び触媒層
５は５５０〜９００℃で運転される。ここで５の部分の
具体的構造としては図２、図３のようなものが実用的で
ある。Hereinafter, the present invention will be described in more detail with reference to examples of the present invention. (Embodiment) An embodiment of the present invention will be described with reference to FIG.
In FIG. 1, 1 is a combustion furnace main body, 2 is a fluidized bed combustion section provided in the combustion furnace main body 1, 3 is a supply line of combustion air, and 4 is a main fuel supplied to the fluidized bed combustion section 2. A certain coal supply line 5 is a dust removal ceramic filter for collecting unburned carbon and an N 2 O decomposition catalyst layer connected to the upper part of the combustion furnace main body 1, and these 5 parts are main constituent elements of the present invention. is there. Generally, the ceramic filter for dust removal and the catalyst layer 5 are operated at 550 to 900 ° C. Here, as a specific structure of the portion 5, those shown in FIGS. 2 and 3 are practical.
【００１３】図２は参考例であり、数百μの粗粒子から
なる骨格層１０１の上層の０．１〜数μの微粒のダスト
除去用のセラミックスフィルタ層１０２の更に上層に、
Ｎ2Ｏ分解触媒層１０３を１０μ〜数ｍｍの厚さでコー
ティングしたものである。また、図３は骨格層１０１の
各粗粒子の表面にＮ2 Ｏ分解触媒の微粒１０４を焼結さ
せたものである。１０２は図２と同じものを意味する。FIG. 2 is a reference example, in which a ceramic filter layer 102 for removing dust of 0.1 μm to several μm above the skeletal layer 101 composed of coarse particles of several hundred μm is further provided.
The N 2 O decomposition catalyst layer 103 is coated with a thickness of 10 μm to several mm. FIG. 3 is a diagram in which fine particles 104 of an N 2 O decomposition catalyst are sintered on the surface of each coarse particle of the skeleton layer 101. 102 means the same as in FIG.
【００１４】こゝにおいて使用した触媒は平均粒径が約
１０μｍのＡｌ2 Ｏ3 にＬａ2 Ｏ3として１０ｗｔ％、
ＣｅＯ2 として５ｗｔ％となるようにそれぞれの硝酸塩
である硝酸ランタン、硝酸セリウムを混合し、これら混
合物を蒸留水に溶解し、約１００℃で２時間蒸発させて
固体を得、これを１０００℃５時間、空気中で焼成する
ことにより得た触媒を使用した。焼成した触媒を粉砕し
て平均粒径約２μｍにしたあと、これにバインダ及び分
散材を添加して触媒水溶液をつくり、図２，図３の除塵
用セラミックスフィルタに塗布焼成して触媒層を形成し
た。[0014] The catalyst used in this test was Al 2 O 3 having an average particle size of about 10 μm, and La 2 O 3 was 10 wt%.
Lanthanum nitrate and cerium nitrate, each of which is a nitrate, are mixed so as to be 5 wt% as CeO 2 , and the mixture is dissolved in distilled water and evaporated at about 100 ° C. for 2 hours to obtain a solid. The catalyst obtained by calcining in air for hours was used. After the fired catalyst is pulverized to an average particle size of about 2 μm, a binder and a dispersing agent are added thereto to form a catalyst aqueous solution, which is applied to the ceramic filter for dust removal shown in FIGS. 2 and 3 and fired to form a catalyst layer. did.
【００１５】いずれの方式でもＮ2 Ｏ低減に有効であ
る。実際的には、このような除塵用セラミックスフィル
タとＮ2 Ｏ分解触媒を一体化した構造物を、円筒状又は
ハニカム状として燃焼排ガスの流炉中に設置することに
より除塵とＮ2 Ｏの分解の２つの目的を達することが可
能である。この場合、両層を通過するガスの線速度は数
ｃｍ〜数十ｃｍ／秒である。 Either method is effective in reducing N 2 O. Practically, by installing such a structure in which the ceramic filter for dust removal and the N 2 O decomposition catalyst are integrated in a cylindrical or honeycomb shape in a flow furnace of the combustion exhaust gas, dust removal and decomposition of N 2 O are performed. It is possible to achieve the two objectives. In this case, the linear velocity of the gas passing through both layers is several cm to several tens cm / sec .
【００１６】[0016]
【発明の効果】本発明によれば排ガス中のＮ 2 Ｏをダス
トと共に除去する方法が提供され、地球温室効果および
成層圏オゾン層破壊の原因物質の一つであるＮ2 Ｏを容
易、低廉、かつ効果的に低減する方法が提供される。According to the present invention, there is provided a method for removing N 2 O in exhaust gas together with dust, and it is possible to easily and inexpensively reduce N 2 O which is one of the causative substances of the global greenhouse effect and the stratospheric ozone layer. And a method for effectively reducing is provided.
【図１】本発明方法の一実施例の説明図。FIG. 1 is an explanatory view of an embodiment of the method of the present invention.
【図２】本発明方法の参考例のＮ2 Ｏ分解触媒と除塵用
セラミックスフィルタの組み合せの説明図。FIG. 2 is an explanatory view of a combination of an N 2 O decomposition catalyst and a ceramic filter for dust removal according to a reference example of the method of the present invention.
【図３】本発明方法の一実施例のＮ2 Ｏ分解触媒と除塵
用セラミックスフィルタの組み合せの説明図。FIG. 3 is an explanatory view of a combination of an N 2 O decomposition catalyst and a dust removing ceramic filter according to one embodiment of the present invention.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 角田 英雄 長崎県長崎市深堀町五丁目717番１号 三菱重工業株式会社長崎研究所内 (72)発明者 守井 淳 長崎県長崎市飽の浦町１番１号 三菱重 工業株式会社長崎造船所内 (72)発明者 小林 敬古 東京都千代田区丸の内二丁目５番１号 三菱重工業株式会社本社内 (72)発明者 内田 聡 東京都千代田区丸の内二丁目５番１号 三菱重工業株式会社本社内 (56)参考文献 特開 平４−341325（ＪＰ，Ａ) 特開 昭48−20791（ＪＰ，Ａ) 特開 平５−15742（ＪＰ，Ａ) 特開 平４−135624（ＪＰ，Ａ) (58)調査した分野(Int.Cl.7，ＤＢ名) B01D 53/86 B01D 53/94 B01J 21/00 - 38/74 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Hideo Tsunoda 5-717-1, Fukahori-cho, Nagasaki-shi, Nagasaki Mitsubishi Heavy Industries, Ltd. Nagasaki Research Laboratory (72) Inventor Jun Morii 1-1-1, Akunoura-cho, Nagasaki-shi, Nagasaki Mitsubishi Heavy Industries, Ltd., Nagasaki Shipyard (72) Inventor Takako Kobayashi 2-5-1 Marunouchi, Chiyoda-ku, Tokyo Mitsubishi Heavy Industries, Ltd. (72) Inventor Satoshi Uchida 2-5-1 Marunouchi, Chiyoda-ku, Tokyo No. Mitsubishi Heavy Industries, Ltd. (56) References JP-A-4-341325 (JP, A) JP-A-48-20791 (JP, A) JP-A-5-15742 (JP, A) JP-A-4- 135624 (JP, A) (58) Field surveyed (Int. Cl. 7 , DB name) B01D 53/86 B01D 53/94 B01J 21/00-38/74
Claims (1)
塵用セラミックスフィルタを設置し、該フィルタの大粒
子骨格層にランタニド元素の酸化物を含むアルミナを主
成分とするセラミックスよりなる亜酸化窒素分解触媒を
小粒子として介在させることを特徴とする燃焼排ガス中
の亜酸化窒素の処理方法。 1. A method for removing exhaust gas in a flue gas passage at 550 ° C. or higher.
Install a ceramic filter for dust,
Alumina containing lanthanide element oxide
Nitrous oxide decomposition catalyst consisting of ceramics as a component
In combustion exhaust gas characterized by inclusion as small particles
For treating nitrous oxide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12582793A JP3202411B2 (en) | 1993-05-27 | 1993-05-27 | Nitrous oxide treatment method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12582793A JP3202411B2 (en) | 1993-05-27 | 1993-05-27 | Nitrous oxide treatment method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH06327973A JPH06327973A (en) | 1994-11-29 |
| JP3202411B2 true JP3202411B2 (en) | 2001-08-27 |
Family
ID=14919928
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP12582793A Expired - Lifetime JP3202411B2 (en) | 1993-05-27 | 1993-05-27 | Nitrous oxide treatment method |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3202411B2 (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3572548B2 (en) | 2002-05-24 | 2004-10-06 | 日本酸素株式会社 | Gas purification method and apparatus |
| EP2048258A1 (en) | 2002-11-20 | 2009-04-15 | Nippon Steel Corporation | Honeycomb bodies employing high Al stainless steel sheet and process for production thereof |
| FR2936718B1 (en) * | 2008-10-03 | 2010-11-19 | Rhodia Operations | METHOD OF DECOMPOSING N2O USING CATALYST BASED ON CERIUM OXIDE AND LANTHANE |
| JP5580568B2 (en) * | 2009-10-16 | 2014-08-27 | 出光興産株式会社 | Active alumina catalyst and method for removing nitrous oxide |
| JP5916470B2 (en) * | 2011-08-04 | 2016-05-11 | 三菱重工業株式会社 | Fluidized bed processing system and N2O removal method of fluidized bed combustion exhaust gas |
-
1993
- 1993-05-27 JP JP12582793A patent/JP3202411B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH06327973A (en) | 1994-11-29 |
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