JP2851451B2 - Method for reducing nitrous oxide in flue gas - Google Patents
Method for reducing nitrous oxide in flue gasInfo
- Publication number
- JP2851451B2 JP2851451B2 JP3071983A JP7198391A JP2851451B2 JP 2851451 B2 JP2851451 B2 JP 2851451B2 JP 3071983 A JP3071983 A JP 3071983A JP 7198391 A JP7198391 A JP 7198391A JP 2851451 B2 JP2851451 B2 JP 2851451B2
- Authority
- JP
- Japan
- Prior art keywords
- nitrous oxide
- flue gas
- gas
- reducing nitrous
- combustion
- 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 - Fee Related
Links
- GQPLMRYTRLFLPF-UHFFFAOYSA-N Nitrous Oxide Chemical compound [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 title claims description 14
- 238000000034 method Methods 0.000 title claims description 7
- 239000001272 nitrous oxide Substances 0.000 title claims description 7
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 title claims description 5
- 239000003546 flue gas Substances 0.000 title claims description 5
- 239000003054 catalyst Substances 0.000 claims description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 239000007789 gas Substances 0.000 description 13
- 238000002485 combustion reaction Methods 0.000 description 12
- 239000003245 coal Substances 0.000 description 5
- 229910017563 LaCrO Inorganic materials 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000009533 lab test Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 229910052573 porcelain Inorganic materials 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000005437 stratosphere Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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（７００〜９００℃）流動床方
式のボイラ、又は都市ゴミ焼却炉等より発生する亜酸化
窒素（Ｎ2 Ｏ）を含む排ガス中の亜酸化窒素の低減方法
に関する。The present invention is for business BACKGROUND OF THE, industrial boiler, particularly low combustion temperature (700 to 900 ° C.) fluidized bed system of the boiler, or nitrous oxide generated from municipal waste incinerators or the like (N 2 The present invention relates to a method for reducing nitrous oxide in exhaust gas containing O).
【０００２】[0002]
【従来の技術】亜酸化窒素（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 Nitrous oxide (N 2 O) has relatively 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. It is the current situation.
【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。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.
【０００４】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（７００〜９０
０℃）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。This N 2 O is generally used at a high temperature (1300 ° C. or higher) for combustion (pulverized coal combustion, gas combustion, oil combustion, etc.).
Hardly occur at low temperatures such as fluidized beds (700-90
(0 ° C.), it is generally accepted that a considerable concentration is generated.
【０００５】本発明は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方法を提供し
ようとするものである。[0005] The present invention relates to N 2 gas contained in exhaust gas once produced.
It is intended to provide a method for efficiently reducing O by simple means.
【０００６】[0006]
【課題を解決するための手段】本発明は燃焼排ガス中の
亜酸化窒素を６００℃以上の領域で、ペロスカイト型酸
化物を触媒として窒素に分解することを特徴とする燃焼
排ガス中の亜酸化窒素の低減方法である。The present invention is characterized in that nitrous oxide in flue gas is decomposed into nitrogen by using a perovskite-type oxide as a catalyst in a temperature range of 600 ° C. or higher. This is a method for reducing the amount of light.
【０００７】本発明でいうペロブスカイト型酸化物と
は、化学式ＡＢＯ3 で示される複合酸化物で、ＬａＣｏ
Ｏ3 ，ＬａＭｎＯ3 ，ＬａＣｒＯ3 ，ＴｉＢａＯ3 な
ど、触媒活性が大きく、酸化雰囲気での耐熱性に優れる
等の、特有の性質を有している。The perovskite oxide referred to in the present invention is a complex oxide represented by the chemical formula ABO 3 ,
O 3 , LaMnO 3 , LaCrO 3 , TiBaO 3, etc. have unique properties such as high catalytic activity and excellent heat resistance in an oxidizing atmosphere.
【０００８】[0008]
【作用】Ｎ2 Ｏは６００℃以上でのペロブスカイト型酸
化物触媒の作用により、実用的な速度及び耐久性を維持
してＮ2 とＯ2 に分解することが本発明者らの実験によ
って判明した。[Action] N 2 O by the action of the perovskite-type oxide catalyst at 600 ° C. or higher, to decompose while maintaining the practical speed and durability to N 2 and O 2 is found by experiments of the present inventors did.
【０００９】以下に本発明者らの実験室試験結果につい
て述べる。Ｎ2 Ｏ ４９ｐｐｍ、Ｏ2 ３％、残部Ｎ2 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Ｎ
2 Ｏの分解挙動を調査した。反応時間は０．４秒、ガス
流量は２Ｎｌ／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。なお、触媒はペレット
状のペロブスカイト型酸化物２０ｇを充填した。The results of the laboratory tests of the present inventors will be described below. A test gas consisting of 49 ppm of N 2 O, 3% of O 2 , and the balance of N 2 was adjusted with a standard gas cylinder and a floating flow meter, and was supplied from a porcelain reaction tube (alumina inner diameter 20 mm, effective heating length 150 mm) and an electric furnace. Using a fluidized reactor
The decomposition behavior of 2 O was investigated. The reaction time was 0.4 seconds, the gas flow rate was 2 Nl / min, and the analysis of the N 2 O concentration was performed by an ECD detector gas chromatograph. The catalyst was filled with 20 g of perovskite oxide in the form of pellets.
【００１０】結果を表１に示す。表１に示したように、
Ｎ2 はＬａＣｒＯ3 あるいはＬａＭｎＯ3 の存在下では
６００℃以上で有効に低減されることが判明した。な
お、出口ガス中のＮＯ、ＮＯ2 濃度は、いずれの条件で
も１ｐｐｍ以下であり、Ｎ2 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,
It has been found that N 2 is effectively reduced at 600 ° C. or higher in the presence of LaCrO 3 or LaMnO 3 . The concentrations of NO and NO 2 in the outlet gas are 1 ppm or less under any conditions, and N 2 O is decomposed into harmless N 2 and O 2 .
【表１】 [Table 1]
【００１１】[0011]
【実施例】本発明の一実施例を図１によって説明する。
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
多孔性セラミックスフィルタであり、６が本発明の主要
構成要素であるペロブスカイト型酸化物触媒の充填層で
あり、一般に多孔性セラミックフィルタ５及びペロブス
カイト型酸化物触媒充填層６は６５０〜９００℃で運転
される。FIG. 1 shows an embodiment of the present invention.
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 supply of coal which is a main fuel supplied to the fluidized bed combustion section 2. line,
Reference numeral 5 denotes a porous ceramic filter connected to the upper portion of the combustion furnace main body 1 for recovering unburned carbon, and reference numeral 6 denotes a packed layer of a perovskite-type oxide catalyst which is a main component of the present invention. The filter 5 and the perovskite-type oxide catalyst packed bed 6 are operated at 650 to 900 ° C.
【００１２】前記の流動床燃焼部２においては、石炭
（豪州炭）が８５０℃の温度、残留酸素濃度３．５％で
燃焼した。石炭供給量は１００kg／時間であり、触媒と
してＬａＣｒＯ3 をペレット状に成形して、空間速度
（ＳＶ）＝１０，０００ｈｒ-1になるように充填した。
図１で８，９はＮ2 Ｏ濃度の第１及び第２計測点であ
り、７は後流へのＮ2 Ｏ除去後排ガスの流路である。In the fluidized bed combustion section 2, coal (Australian coal) was burned at a temperature of 850 ° C. and a residual oxygen concentration of 3.5%. The amount of coal supplied was 100 kg / hour, and LaCrO 3 was formed into a pellet shape as a catalyst and charged so as to have a space velocity (SV) of 10,000 hr −1 .
In FIG. 1, reference numerals 8 and 9 denote first and second measurement points of the N 2 O concentration, and reference numeral 7 denotes a flow path of the exhaust gas after removing the N 2 O to the downstream.
【００１３】以上の方法により、多孔性フィルタ５の入
口濃度７３ｐｐｍのＮ2 Ｏを２．５ｐｐｍまで低減させ
ることができた。また排ガス中に含まれるＳＯ2 の濃度
は４５ｐｐｍであったが、これに被毒されることもな
く、１８００時間後の性能は初期と殆ど差がなく、耐久
性にも問題がないことが確認された。By the above method, N 2 O at the inlet concentration of the porous filter 5 of 73 ppm could be reduced to 2.5 ppm. Although the concentration of SO 2 contained in the exhaust gas was 45 ppm, it was confirmed that there was no poisoning, the performance after 1800 hours was almost the same as the initial one, and there was no problem in durability. Was done.
【００１４】[0014]
【発明の効果】以上説明したように、本発明はＮ2 Ｏを
含む燃焼排ガス中の６００℃以上の領域にペロブスカイ
ト型酸化物触媒層を設置するという簡単な手段によっ
て、地球温室効果および成層圏オゾン層破壊の原因物質
の一であるＮ2 Ｏを容易、低廉、かつ効果的に低減する
ことができる。As described above, the present invention provides the global greenhouse effect and stratospheric ozone by a simple means of installing a perovskite-type oxide catalyst layer in a region of 600 ° C. or higher in a flue gas containing N 2 O. N 2 O, which is one of the substances causing layer destruction, can be easily, inexpensively, and effectively reduced.
【図１】本発明の一実施例の説明図。FIG. 1 is an explanatory diagram of one embodiment of the present invention.
───────────────────────────────────────────────────── フロントページの続き (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 (56)参考文献 特開 昭63−7826（ＪＰ，Ａ) 特開 昭56−11067（ＪＰ，Ａ) 特開 昭48−55893（ＪＰ，Ａ) (58)調査した分野(Int.Cl.6，ＤＢ名) B01D 53/94 B01J 23/26 B01J 23/34──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Keiko Kobayashi 2-5-1 Marunouchi, Chiyoda-ku, Tokyo Mitsubishi Heavy Industries, Ltd. Head Office (56) References JP-A-63-7826 (JP, A) JP-A-56-11067 (JP, A) JP-A-48-55893 (JP, A) (58) Fields investigated (Int. Cl. 6 , DB name) B01D 53/94 B01J 23/26 B01J 23/34
Claims (1)
上の領域で、ペロブスカイト型酸化物を触媒として窒素
に分解することを特徴とする燃焼排ガス中の亜酸化窒素
の低減方法。1. A method for reducing nitrous oxide in flue gas, comprising decomposing nitrous oxide in the flue gas into nitrogen using a perovskite oxide as a catalyst in a region of 600 ° C. or higher.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3071983A JP2851451B2 (en) | 1991-04-05 | 1991-04-05 | Method for reducing nitrous oxide in flue gas |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3071983A JP2851451B2 (en) | 1991-04-05 | 1991-04-05 | Method for reducing nitrous oxide in flue gas |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH05269352A JPH05269352A (en) | 1993-10-19 |
| JP2851451B2 true JP2851451B2 (en) | 1999-01-27 |
Family
ID=13476209
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3071983A Expired - Fee Related JP2851451B2 (en) | 1991-04-05 | 1991-04-05 | Method for reducing nitrous oxide in flue gas |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2851451B2 (en) |
-
1991
- 1991-04-05 JP JP3071983A patent/JP2851451B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH05269352A (en) | 1993-10-19 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 19981006 |
|
| LAPS | Cancellation because of no payment of annual fees |