JP2004198099A - 多用途用および産業用炉システムにおける低温腐食と高温腐食の両方の抑制でマンガン化合物を使用 - Google Patents
多用途用および産業用炉システムにおける低温腐食と高温腐食の両方の抑制でマンガン化合物を使用 Download PDFInfo
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Abstract
【解決手段】 本発明は、燃焼システムにマンガンまたはマンガン前駆体源または誘導体を有効量で添加することで大気バーナーユニットの腐食を軽減または抑制することに関する。前記システムに更に触媒パッケージを含めることができ、そしてその触媒パッケージをLi、Na、K、Mg、Ca、Sr、Ba、Mo、Fe、Co、Pt、Ceの1種以上の個々の有機金属化合物またはこれらの組み合わせ、混合物または前駆体で構成させることができる。本発明の触媒パッケージに含有させたマンガン成分は前記燃焼システムの効力低下を軽減またはなくし、その結果として、燃焼を向上させかつ放出物量を減少させる。加うるに、本発明は、バーナー炉の壁および管の熱い表面およびバーナーユニットの排気用煙突の冷えた表面で起こる高温腐食と低温腐食の両方も抑制する。
【選択図】 なし
Description
炭素/炭化水素焼失および一酸化炭素除去
大部分の有機金属含有燃料添加剤は炎の中で分解して個々の金属原子を生成する。燃焼時の燃料と空気の混合レベルは不均一である、と言うのは、燃料を注入している間に着火が起こりかつ燃料を注入しながら燃焼熱が燃料中心部に放射されて戻り、それによって、そのように燃料が豊富なゾーンの中で燃料の熱分解反応が起こるからである。そのような熱分解生成物が煤核形成部位を形成し、それが凝固および凝集機構で成長して目に見える煤になる。燃焼が起こっている時、マンガンを含有する燃料添加剤が熱分解を起こすことで生じたマンガン原子が互いにおよび燃料熱分解生成物(これは凝固および凝集して目に見える煤になっている)と衝突する。その金属原子はまた下記の図式的反応に従って酸素とも衝突する。
M(原子)+1/2O2→MO
そのような燃焼環境下で起こる金属原子(即ちPt、Fe、Ce、Mnなど)間の如何なる衝突も非弾性的(これは「裸の」金属原子が衝突する性質である)であり、それによって、燃焼ガス中の金属の分散度が低くなる。しかしながら、燃料熱分解生成物が凝集しながら金属原子と衝突すると粒子が帯電することで分散が維持され、その結果として、煤粒子は高度に分散した金属原子およびこれらの束(これは煤粒子と衝突する前に生じる可能性がある)と衝突する。このような過程が起こると混合レベルが高くなり、そして温度が400℃を超えると、煤が熱で酸化を受ける速度が酸素がそのような粒子と衝突する速度と同じになる。その酸化の速度は温度に依存し、温度が400℃未満になると遅くなる。しかしながら、粒子が金属原子と衝突すると、下記の式に示すように、炭素の酸化が二酸化炭素と金属触媒種による触媒作用を受けることが理由で酸化が高い速度で持続する。
MOx+CO→MOx−1(cat)+CO2
C(煤粒子上)+CO2+MOx−1(cat)→2CO+MOx−1(cat)
MOx−1(cat)+1/2O2→MOx
この上に示した3式に従ってそのような金属酸化物による触媒作用を受ける「炭素焼失(carbon burnout)」反応は250℃の如き低い温度でも持続し得る。最後に、そのようにして生成した一酸化炭素はさらなる酸化を受けて二酸化炭素になる、と言うのは、時間と共に混合レベルが高くなることが理由で燃焼混合物に入っている酸素の豊富度が高くなるからである。それによって、反応式
MOx−1(cat)+1/2O2→MOx
MOx+CO→MOx−1(cat)+CO2
に従い、MOxの濃度が増進する。この上に示した反応サイクルは酸素濃度に依存し、温度が250℃の如く低くなっても燃焼ガスの中で起こり続ける。燃料媒介有機金属触媒、例えばPt、Fe、Ceなどから誘導された化合物などが触媒作用を及ぼすそのような炭素焼失、炭化水素酸化および二酸化炭素除去反応は、燃料成分に入っている硫黄、燐、バナジウム、鉛など(これらはそのような触媒と反応して触媒を失活させる)で抑制され得る。
触媒活性の最適化および低温腐食の防止
炭化水素系燃料の燃焼で生じた三酸化硫黄(SO3)は、排気の温度が水の露点より低い温度にまで冷えると、水蒸気と結合して硫酸を生じる。そのような酸が存在すると結果として排気装置の低温腐食と腐食性環境汚染(酸性雨)の両方がもたらされてしまう。大気(固定式)バーナーの場合、排気装置の腐食は修復費用および停止時間の意味で極めて重要であり得る。燃料媒介金属触媒は二酸化硫黄(SO2)から三酸化硫黄への転化速度を非常に速くする。このような反応のいくつかの効率を以下に示す。
[Joint Power Generation Conference(フェニックス、アリゾナ、1980年9月28日から10月2日)におけるASMEプレゼンテーションであるGray,M.A.、「The Effect of a Volatile Fireside Manganese Additive on Coal−Fired Utility Boiler Operation」]。
高温腐食
本分野の技術者は、使用燃料にナトリウム(Na)および/またはバナジウム(V)が入っていると高温で腐食が起こることを予測し得るであろう、と言うのは、温度が550から680℃の範囲になると用役用炉表面に前記種の高腐食性複合酸化物、例えば「5Na2O・V2O4・11V2O5」(バナジルバナジン酸ナトリウム)などが生じるからである。そのような低融点酸化物は1)SO2からSO3への転化用触媒そして2)酸素を気相からユニットの鉄表面に移送する触媒として効力を示す。燃料媒介触媒(Pt、Fe、Ceなど)と一緒に添加したマンガン共触媒はそのような表面付着物から酸素を優先的に捕捉してそれを炭素焼失反応で利用させるであろう。それによって、融点が高い方のバナジルバナジン酸ナトリウムから融点が低くて腐食性がより高い類似物(これは多用途用炉およびパイプの表面と一緒に共晶フラックスを形成することにより高温腐食の一因になり、その結果として、表面の侵食が起こる)への酸化が抑制されるであろう(例えばPollman,S、Mineralogisch kristallographische Untersuchungen an Schlaken und Rohrbelagen aus dem Hochtemperaturbereich olgefeuerter Groβkessel、VGB−Mitteilungen、94、1頁、1965、Volker Hoenig,L.、「Untersuchung der Wirkungsmechanismen von Additiven fur shweres Heizol」、Fortschritt−Berichte VDI、Reihe 15、Umwelttechnik、Nr.84、57−59頁およびそこに引用されている文献、Dusseldorf.VDI−Verlag 1991、そしてWahnschaffe,E.、Kontinuierliche SO3−und Taubereichsmessunged auf olgefeurten Dampferzuegern.Mitteilungen der VGB、Heft 3、193頁、1968を参照)。
Claims (13)
- 燃料を燃焼させる燃焼ユニットの腐食を抑制する方法であって、前記燃焼にマンガン源を腐食抑制量で添加することを含んで成る方法。
- 前記腐食が400℃より高い温度で起こる請求項1記載の方法。
- 前記腐食が250℃以下の温度で起こる請求項1記載の方法。
- バナジウム含有燃料が燃焼ユニットの中で燃焼する結果生成する飛散灰中のバナジウムの量を減少させる方法であって、前記燃料またはその燃焼生成物にマンガン源をこれが前記バナジウムもしくはその燃焼生成物と結合するに有効な量で添加することにより生成する飛散灰中のバナジウムの量を減少させることを含んで成る方法。
- 鉄含有燃料が燃焼ユニットの中で燃焼する結果生成する飛散灰中の鉄の量を減少させる方法であって、前記燃料またはその燃焼生成物にマンガン源をこれが前記鉄もしくはその燃焼生成物と結合するに有効な量で添加することにより生成する飛散灰中の鉄の量を減少させることを含んで成る方法。
- 硫黄含有燃料が燃焼ユニットの中で燃焼する結果生成する飛散灰中の硫黄の量を減少させる方法であって、前記燃料またはその燃焼生成物にマンガン源をこれが前記硫黄もしくはその燃焼生成物と結合するに有効な量で添加することにより生成する飛散灰中の硫黄の量を減少させることを含んで成る方法。
- Li、Na、K、Mg、Ca、Sr、Ba、Mo、Fe、Co、Pt、Ceから成る群から選択される少なくとも1種の元素およびこれらの組み合わせ、混合物および前駆体を含有する1種以上の燃料媒介放出物制御用有機金属触媒化合物が硫黄、バナジウム、鉄および燐から成る群から選択される少なくとも1種の汚染物質を有する炭化水素系燃料が燃焼ユニットの中で起こす燃焼の中に存在するか或は前記燃焼に由来する三酸化硫黄の生成の制御で示す効率を向上させる方法であって、前記少なくとも1種の汚染物質を充分な量のマンガンもしくはその源と化合させることを含んで成る方法。
- 燃料を燃焼させる燃焼ユニットの中に存在していて前記燃焼の生成物にさらされるFe2O3含有金属表面を不活性化する方法であって、前記金属表面が不活性化されるように前記燃焼にマンガンまたはその源をマンガンがFe2O3の少なくともいくらかを還元してFe3O4を生成させるに充分な量で添加することを含んで成る方法。
- 燃料を燃焼させる燃焼ユニットの中のある表面で起こるFe3O4からFe2O3への酸化を抑制する方法であって、Fe3O4からFe2O3への酸化が抑制されるように前記燃焼にマンガン源をマンガンが酸素を捕捉するに充分な量で添加することを含んで成る方法。
- 燃料を燃焼させそしてそれによって炭素含有飛散灰が生成する燃焼ユニットの電気式集じん装置の効率を向上させる方法であって、前記燃焼にマンガン源を前記電気式集じん装置への炭素の付着が減少しかつ電気式集じん装置の効率が向上するに充分な量で添加することを含んで成る方法。
- 前記燃焼ユニットがいずれかおよびあらゆるバーナーまたは燃焼装置、固定式バーナー、廃棄物焼却炉、ディーゼル燃料バーナー、ガソリン燃料バーナー、パワープラントジェネレーター、パワープラント炉、いずれかおよびあらゆる内部および外部燃焼装置、ボイラー、炉、蒸気バーナー、プラズマバーナーシステム、プラズマアーク、及び炭化水素系燃料を燃焼させ得るか或は炭化水素系燃料が中で燃焼し得る装置から成る群から選択される請求項1−10のいずれか1項記載の方法。
- 前記燃料がディーゼル燃料、バイオディーゼル、バイオディーゼル誘導燃料、合成ディーゼル、ジェット燃料、アルコール、エーテル、ケロセン、低硫黄燃料、合成燃料、Fischer−Tropsch燃料、液体石油ガス、石炭から誘導された燃料、石炭、遺伝子工学で作られたバイオ燃料および作物およびそれらから抽出された抽出液、天然ガス、プロパン、ブタン、無鉛モーターおよび航空ガソリン、ガソリン沸騰範囲の炭化水素と燃料に可溶な酸素化ブレンド剤の両方を含有する改質ガソリン、ガソリン、バンカー重油、石炭(塵またはスラリー)、原油、製油所の「釜残」および副生成物、原油抽出液、有害な廃棄物、ヤードトリミングおよび廃棄物、ウッドチップおよび鋸屑、農業廃棄物、かいば、飼料、プラスチック、有機廃棄物およびそれらの混合物、そしてそれらが水、アルコールおよび他の担体流体に入っている乳液、懸濁液および分散液から成る群から選択される請求項1−11のいずれか1項記載の方法。
- 前記マンガンがメチルシクロペンタジエニルマンガントリカルボニル、シクロペンタジエニルマンガントリカルボニル、ビス−シクロペンタジエニルマンガン(マンガノセン)、ビス−アルキルシクロペンタジエニルマンガン、スルホン酸マンガン、マンガンフェネート、サリチル酸マンガン、アルキルシクロペンタジエニルマンガントリカルボニル、有機マンガントリカルボニル誘導体、アルキルシクロペンタジエニルマンガン誘導体、中性および過塩基サリチル酸マンガン、中性および過塩基マンガンフェネート、中性および過塩基スルホン酸マンガン、カルボン酸マンガンおよびそれらの組み合わせおよび混合物から成る群から選択される請求項1−12のいずれか1項記載の方法。
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US10/322,158 US8257450B2 (en) | 2002-12-18 | 2002-12-18 | Manganese compounds to inhibit both low-and high-temperature corrosion in utility and industrial furnace systems |
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JP (1) | JP2004198099A (ja) |
CN (1) | CN100584931C (ja) |
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JP2008115459A (ja) * | 2006-11-03 | 2008-05-22 | Korea Electric Power Corp | 燃料添加剤によるガスタービン高温部品の耐食・耐酸化コーティング層形成方法 |
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AU2003241646A1 (en) | 2004-07-08 |
CN1508235A (zh) | 2004-06-30 |
SG112890A1 (en) | 2005-07-28 |
ATE483782T1 (de) | 2010-10-15 |
EP1431372B1 (en) | 2010-10-06 |
CN100584931C (zh) | 2010-01-27 |
DE60334434D1 (de) | 2010-11-18 |
US8257450B2 (en) | 2012-09-04 |
CA2437845A1 (en) | 2004-06-18 |
EP1431372A2 (en) | 2004-06-23 |
EP2199374A2 (en) | 2010-06-23 |
EP1431372A3 (en) | 2004-10-27 |
US20040118032A1 (en) | 2004-06-24 |
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