臺灣博碩士論文加值系統

本文以儲存安全性較佳以及逸散毒性較弱的一氧化碳(CO)替代氨(NH3)作為還原劑，在較廉價的銅活性碳觸媒作用下進行一氧化氮(NO)之還原反應。採用椰殼活性碳為原料，經硝酸處理後含浸於一定濃度的硝酸銅水溶液中，利用化學含浸法製成銅活性碳觸媒(1.1 mmol/g Cu/AC)。再將觸媒置於固定床式反應器中，通入含NO、CO及He之反應氣體，進行NO還原性能測試。
研究結果顯示在無氧條件下進行NO還原反應時，發現添加CO對增加NO轉化率的影響非常明顯，當CO對NO的添加比例增至四比一時(COi：NOi＝1440ppm：360ppm)，在270℃的低溫下NO轉化率即可達97%。添加CO可減少觸媒表面活性基的消耗，有助於觸媒壽命的延長。利用電子顯微鏡(SEM)可觀測到當觸媒喪失活性時，其表面有燒失現象發生而呈現蜂巢狀之構造。於動力學的研究顯示總反應方程式中，各反應物濃度的反應階數與反應溫度有關，其代表NO濃度的反應階數隨反應溫度增加而增加；而代表CO濃度的反應階數則隨反應溫度增加至270℃時達到最大，顯示此時添加CO對反應的助益最大，但當反應溫度達360℃時代表CO濃度的反應階數降為0.06，表示在此溫度下添加CO對反應之影響已可忽略。

The reducer (i.e. NH3) of the nitrogen monoxide (NO) reduction is replaced by carbon monoxide (CO) over a cheaper copper activated carbon catalyst in this study.The purposes are to improve the storage safety and reduce the slipping toxicity of NH3, and to develop a cheaper NO reduction technology. After acid treating with nitric acid, a coconut activated carbon is adding into the solution of copper nitrate, the copper activated carbon catalyst (i.e. 1.1 mmol/g Cu/AC) is then prepared through chemical impregnation. The NO conversion characteristics of the catalyst are testing at a fixed bed reactor with the reacting gases contained NO, CO,and He.
A significant improvement on the NO conversion is discovered when CO is adding into the NO reduction reaction without O2. Under the reaction condition with the ratio of NO to CO equal to 4:1 (i.e, COi：NOi＝1440ppm：360ppm), the NO conversion is found to be 97% on the temperature 270℃. The addition of CO can reduce the consumption of the surface active sites therefore helpful to last the catalyst life. Through using SEM, the burn-off phenomena and honeycomb structures are discovered on the surface of the catalysts which results the catalyst losing its activity. The kinetic study of the overall reaction equation of NO with CO shows that the reaction order of NO is increasing with the temperature, and the reaction order of CO is reaching to a maximum value at the temperature 240℃. More over, the reaction order of CO is decreasing to 0.06 at 360℃, revealing the effect of adding CO is negligible no effect on NO conversion at such temperature.

摘 要 i
Abstract ii
致謝 iii
目 錄 iv
表目錄 vi
圖目錄 vii
第一章 緒論 1
1-1 前言 1
1-2 研究目的 4
第二章 文獻回顧 5
2-1 氮氧化物之特性 5
2-2 氮氧化物之處理方式 5
2-2-1 非選擇性觸媒還原法 6
2-2-2 選擇性觸媒還原法 7
2-3 活性碳之特性 8
2-3-1 活性碳之結構與組成 8
2-3-2 活性碳之官能基 9
2-3-3 活性碳的種類 11
2-3-4 活性碳之製造 12
2-4 活性碳觸媒在NO還原反應之應用 13
2-4-1 活性碳觸媒除NO之反應 13
2-5 觸媒反應動力學模式 15
2-5-1 Power-rate Law 15
第三章 實驗方法 17
3-1 實驗設備及藥品 17
3-1-1 藥品 17
3-1-2 氣體 17
3-1-3 實驗設備 18
3-2 實驗研究方法 23
3-2-1 銅活性碳觸媒製作 23
3-2-2 觸媒性能測試： 26
3-2-3 測試反應前後觸媒表面之變化： 29
3-2-4 反應動力學研究： 30
第四章 結果與討論 32
4-1 無氧反應時CO對NO的添加比例對觸媒的NO轉化率之影響 32
4-2 添加CO對觸媒壽命的影響 34
4-3 觸媒之NO還原反應路徑 35
4-4 反應前後觸媒SEM影像分析 36
4-5 無氧反應且添加CO時的總反應方程式 38
第五章 結論 46
參考文獻 47
附錄A：質量流量計校正圖 51
附錄B：實驗數據 53
附錄C：總反應方程式之實驗套適 57

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