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研究生:梁煜申
論文名稱:鈀觸媒處理焚化廢氣中CO、NO之動力研究
指導教授:魏銘彥
學位類別:碩士
校院名稱:國立中興大學
系所名稱:環境工程學系
學門:工程學門
學類:環境工程學類
論文種類:學術論文
論文出版年:2003
畢業學年度:91
語文別:中文
論文頁數:127
中文關鍵詞:觸媒焚化前驅物CONO動力研究
外文關鍵詞:Catalytic incinerationsol-gel methodprecursorCONOkinetics
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利用焚化之方式處理廢棄物為垃圾有效之方法之一,其具有去毒性、減容、安定化等優點,然而焚化廢氣之處理亦為重大課題之一,若沒有經由妥善之處理則會對環境造成重大之污染,進而破壞生態之平衡。觸媒焚化已經廣泛應用於空氣污染之防治上,其具有較低溫下可進行反應,且其可減少燃料的消耗並減低氮氧化物的生成。
本研究為使用自行製備之鈀觸媒來處理焚化廢氣中常見之CO及NO,利用不同之擔體前驅物所製備之觸媒來探討其結構及催化焚化廢氣效果上之差異,並進行其相關之動力研究。本研究之內容如下:
1. 利用溶膠-凝膠法(sol-gel method)製備出CeO2/Al2O3之擔體,再經由含浸法將擔體含浸至鈀之前驅物水溶液中,再經由乾燥、鍛燒等步驟製備所需之觸媒,本研究亦探討不同前驅物其所製備之擔體結構上之差異,以BET之結果得知,利用無機前驅物所製備出之觸媒擔體其比表面積及平均孔徑皆較使用有機前驅物來得大。
2. 在不同之操作條件上,整體而言,無機前驅物觸媒之活性勻較有機前驅物觸媒之活性來得佳,證明不同前驅物所製備之相同觸媒其差異亦甚大。
3. 在觸媒忽略質傳條件下,利用plug flow之積分反應器結合Mars and van Krevelen model來求出觸媒之活化能,其結果之迴歸值甚佳,故亦符合其模式之假設。
4. 利用有效因子法求出觸媒在具孔洞擴散阻力之有效因子 值,結果顯示無機前驅物之觸媒在相同之操作條件下其 值較有機前驅物之觸媒來得大,亦因其結構上之差異而造成。
5. 本研究亦探討利用鈀觸媒同時去除CO及NO之可能性,結果顯示NO欲有較高之去除率則需存在有CO濃度較高之情況下,但此卻存在著CO過剩之問題。故將來應用於同時CO及NO時則須在觸媒反應器後再加裝處理CO之空氣污染防治設備。
Municipal solid waste incineration (MSWI) that is considered as an effective method for dealing with solid waste causes a certain air pollutants, such as CO、NO and organic compounds. Currently, the novel technology for NO and CO treatment are by catalytic incineration, which can be operated at low temperature and prevent the thermal NOx generation.
The primary objective at present work is to study the possibility of removing CO and NO simultaneously by Pd/CeO2/Al2O3 catalyst. The CeO2/Al2O3 support was prepared by sol-gel method which using organic and inorganic precursors. Besides, this study also discussed the kinetic behavior of CO oxidation over Pd catalyst. The explanation of results can be divided into few parts.
(1) The different precursor would make different structure of catalyst. In this study, the inorganic precursor catalyst showed a larger BET surface area and pore size.
(2) The inorganic precursor catalyst showed a better activity in CO conversion than organic ones. Hence, the choosing of precursors is also an important parameter.
(3) Integral reactor of plug flow combining Mars-Van Krevelen Model could proper explain the behavior of catalyst. Besides, this study also found the effectiveness factor of catalysts.
(4) Under the SR ratio of CO/NO more than one, NO could be reduced to N2. However, this treatment would have the problem of excess CO. If this method can be applied in the future, another reactor of removal CO should be connected behind NO conversion reactor to prevent the CO pollution.
摘要 I
ABSTRACT III
圖目錄 VIII
表目錄 X
第一章 前言 1
1-1 研究緣起 1
1-2 研究動機與目的 2
1-3 研究流程 2
第二章 文獻回顧 6
2-1 酸性氣體 6
2-1-1 酸性氣體之來源與生成特性 6
2-1-2 酸性氣體之來源及生成行為 7
2-2 一氧化碳(CO) 10
2-2-1 一氧化碳之危害性 10
2-2-2 一氧化碳之生成行為 11
2-3 氣狀污染物之處理技術 13
2-4 觸媒焚化之特性 15
2-4-1 觸媒焚化之原理與反應機制 15
2-4-2 觸媒焚化系統之應用 16
2-4-3 影響觸媒焚化去除效率之因素 17
2-4-4 觸媒製備條件之探討 20
2-4-4-1 觸媒的種類與特性比較 20
2-4-4-2 擔體對觸媒活性之影響 21
2-4-4-3 助促劑(Promoter)對觸媒活性之影響 22
2-4-4-4 觸媒活性衰退 24
2-4-5 觸媒之製備方法 26
2-4-5-1 沈澱法(precipitation) 26
2-4-5-2 含浸法(impregnation) 26
2-4-5-3 溶膠-凝膠法(sol-gel) 27
2-5 觸媒反應機制之探討 33
2-5-1 膜阻力、孔阻力與一次反應之總效應之結合 33
2-5-2 膜阻力控制(Film Resistance Control) 35
2-5-3 孔洞擴散阻力控制(proe diffustion resistance) 35
2-5-4 表面現象阻力(Surface phenomenon resistance): 36
2-5-5 Mars-Van Krevelen model 36
2-5-6 Plug Flow Reactor 38
2-5-6-1 Plug Flow Reactor之微分反應器 38
2-5-6-2 Plug Flow Reactor之積分反應器 39
2-6 文獻總結及研究方向 40
第三章 實驗設備及方法 42
3-1 實驗設備 42
3-1-1 觸媒反應系統 42
3-1-2 觸媒製備 46
3-1-2-1 CeO2/Al2O3 擔體的製備 46
3-1-2-2 觸媒的製備 50
3-1-2-3 樣品分析儀器 50
3-2 實驗試程規劃及流程 51
3-2-1 實驗試程規劃 51
3-3 觸媒研究分析 58
3-3-1觸媒鑑定 58
第四章 結果與討論 65
4-1 觸媒特性分析 65
4-1-1 BET比表面積與平均孔徑測定 65
4-1-2 XRPD物種分析 73
4-1-3 掃描式電子顯微鏡(SEM)表面型態分析 77
4-2 觸媒焚化對CO轉化之動力探討 82
4-2-1 不同製備條件對CO去除之影響 82
4-2-2 空間速度對觸媒處理CO之影響 85
4-2-3 氧濃度對觸媒處理CO之影響 86
4-2-4 操作氣速對觸媒處理CO之影響 89
4-2-5 觸媒粒徑對觸媒處理CO之影響 91
4-2-6 操作溫度對觸媒處理CO之影響 93
4-2-7 積分反應器結合Mars-Van Krevelen Model求取活化能 94
4-2-8 結合氣膜擴散、孔洞擴散及表面反應之探討 97
4-2-9 觸媒同時去除NO、CO之去除可能性之探討 99
4-2-10 助促劑CeO2對觸媒活性之影響 101
4-2-11 實驗再現性之評估 103
第五章 結論與建議 105
5-1 結論 105
5-2 建議 107
參考文獻 108
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